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Download as PDF, TXT or read online from Scribd. Flag for inappropriate content. Uploaded by johnabate24. Anzenbacher Arno Wprowadzenie do. The Messengers from the Hereafter: The End of the World from the Perspective of Arabic dream-books) 208 Pages. Nature and humans because of the free decision of creator. 'We want to set an industry standard for electromobility,' said Arno Antlitz, Volkswagen board member for controlling and accounting. The financial resources for future investments should be generated from the core business, but declining sales, especially in the domestic market of Germany and the growth market of China are. Arno antlitz dissertation writing. Arno antlitz dissertation writing. 5 stars based on 95 reviews. An essay on liberation pdf creator, renaissance medicine research paper. Essay about king arthur farewell Essay about king arthur farewell. Europe without borders essay. ITRDUCTI rganometallic Systems To Sustain A Better Future Almost all branches of chemistry and material science now interface with rganometallic Chemistry. Rganometallics are used extensively in the synthesis. Equazioni Fratte Esercizi Pdf Creator. 4/24/2017 0 Comments. Esercizi sulle equazioni fratte - maggio 2010 Francesco Daddi – Liceo “Falchi” Montopoli in Val d’Arno Esercizio 1. Non sono invece irrazionali (sebbene alcuni coefficienti siano irrazionali) equazioni come la seguente. Powered by Create your own unique website with. Arno Anzenbacher Pdf Creator. 0 Comments The recognition capabilities of acyclic pyridine-based receptors toward monosaccharides were evaluated. Aminopyridine receptors based on the 2,4,6-trimethyl- or 2,4,6-triethylbenzene frame show high β vs α binding selectivity in the recognition of glucopyranosides. Amidopyridine receptors.
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2 ITRDUCTI rganometallic Systems To Sustain A Better Future Almost all branches of chemistry and material science now interface with rganometallic Chemistry. rganometallics are used extensively in the synthesis of useful compounds on both large and small scales. Industrial processes involving plastics, polymers, electronic materials, and pharmaceuticals all depend on advancements in organometallic chemistry. Many catalytic and non-catalytic stereoselective processes that are key steps in creative and non-conventional synthesis of complex molecules have gained significant advantage from organometallic chemistry. The ISC series is the most important school on organometallic chemistry at the European level, organized under the auspices of EuCheMS (the European Association for Chemical and Molecular Sciences) and the interdivisional group of organometallic chemistry of the Italian Chemical Society with the aim of encouraging the presence of young researchers and Ph.D. students both from University and Industry, including those not directly involved in organometallic research projects, in order to bring together young researchers and distinguished European scientists as a contribution to the important goal of increasing the transfer of knowledge at a high level between different European countries and different generations of Scientists. The major objective of the ISC is to promote synergy in organometallic research. The number of participants will be limited to around 120 in order to facilitate maximum interaction among the participants and between them and the lecturers. The 9th edition of ISC (ISC 2013) will focus on the relevance of organometallics systems to sustain a better future. The development of advanced methodologies based on the peculiar properties of organometallic compounds may lead to important changes in the approach of organometallic chemists to the field. A full roster of scientifically distinguished speakers will present their reading keys. In fact, fundamental studies on the mechanistic and structural aspects, as well as new experimental methods and investigation techniques, support the use of organometallic compounds in different application areas including rganometallic Catalysis, Bioorganometallic Chemistry in Biology and Medicine, Green Chemistry (energy and sustainable development), Industrial chemistry and Polymers production, Metal-mediated organic synthesis and Activation of small molecules. Camerino The town of Camerino, with about 7,500 inhabitants today, is located 661 meters above sea level, on the dorsal that separates the valley of Chienti from that of Potenza, in the heart of Marche. f pre-roman origin the town has played an important political and ecclesiastical role through the centuries reaching a notable level of economic and civil development. The wealth of monuments and the vivacity of university life, that pulsates there for almost 700 years, make Camerino a significant center of culture and art.
3 TIMETABLE Friday 15,30 16,00 17,30 18,00 30 August pening Session Prof. K. Tatsumi Coffee break Prof. Eisenstein Saturday 9,00 10,30 11,00 31 August Prof. P. J. Sadler Coffee break Prof. E. A. Quadrelli 14,30 16,00 16,30 Prof. C. ájera Domingo Coffee break Prof. E. Schulz 18,00 19,30 21,00 Flash Presentations Poster session Welcome Dinner Sunday 8,30 10,00 11,30 12,00 1 September Prof. D. Milstein Prof. M. Albrecht Coffee break Prof. J. Clayden 15,00 20,00 Social Excursion Social dinner Monday 9,30 11,00 11,30 2 September Prof. P. J. Pérez Coffee break Prof F. Ruffo 15,00 16,30 17,00 18,00 Prof. A. S. K. Hashmi Coffee break Flash Presentations Poster Session Tuesday 9,00 10,00 10,30 12,00 3 September Prof V. Cadierno Menéndez Coffee break Prof. G. Reginato Prizes and Closing Ceremony
4 PRGRAMME Friday, 30 August: 15,30: pening Session 16,00: Prof. K. Tatsumi rganometallic chemistry of reductases - A clue to building a future sustainable society 17,30: Coffee break 18,00: Prof. Eisenstein lefin metathesis catalysis with d0 Schrock metal alkylidene complexes: the input from computational studies Saturday, 31 August: 9,00: Prof. P. J. Sadler rganometallic anticancer complexes with new mechanisms of action 10,30: Coffee break 11,00: Prof. E. A. Quadrelli Dinitrogen hydrogenation & cleavage an route to H3 with a surface coordination chemistry perspective 14,30: Prof. C. ájera Domingo Coinage metal complexes as chiral catalysts for 1,3-dipolar cycloadditions 16,00: Coffee break 16,30: Prof. E. Schulz Hydroamination reactions of unactivated olefins 18,00: Flash Presentations 19,30: Poster session 21,00: Welcome Dinner Sunday, 1 September: 8,30: Prof. D. Milstein Sustainable catalysis based on pincer complexes 10,00: Prof. M. Albrecht Strong donor carbenes and their potential in (oxidation) catalysis 11,30: Coffee break 12,00: Prof. J. Clayden ew reactivity from organolithiums 15,00: Social Excursion 20,00: Social dinner Monday, 2 September: 9,30: Prof. P. J. Pérez Catalytic Functionalization of Hydrocarbons: the Methane Problem 11,00: Coffee break 11,30: Prof. F. Ruffo Sweetness and privilege of metal promoted asymmetric catalysis 15,00: Prof. A. S. K. Hashmi Gold catalysis - A universe of innovation 16,30: Coffee break 17,00: Flash Presentations 18,30: Poster session Tuesday, 3 September: 9,00: Prof. V. Cadierno Menéndez Metal-catalyzed amide bond forming reactions in water: itrile hydrations and beyond 10,00: Coffee break 10,30: Prof. G. Reginato Advances in cross coupling reactions. Synthetic applications in the field of new generation solar cells 12,00: Prizes and Closing Ceremony
5 RGAIZIG CMMITTEE Augusto CIGLAI Claudio PETTIARI Fabio MARCHETTI Honorary President of ISC Chair Co-chair Riccardo PETTIARI Corrado DI ICLA Adriano PIZZABICCA Roberto BALLII Marino PETRII Enrico MARCATI Advisory Board Pierre BRAUSTEI (University of Strasbourg, France) Ernesto CARMA (University of Sevilla, Spain) Kees ELSEVIER (University of Amsterdam, etherlands) Josè GIME (University of viedo, Spain) Roberto GBETT (University of Torino, Italy) Helena GREBERG (Uppsala University) Giovanni ATILE (University of Bari, Italy) Luis A. R (University of Zaragoza, Spain) Robin. PERUTZ (University of York, UK) Maurizio PERUZZII (ICCM-CR, Firenze, Italy) Claudio PETTIARI (University of Camerino, Italy) Giovanni PLI (P. M. Curie University, Paris, France) Rinaldo PLI (LCC, CRS, Toulouse, France) Armando PMBEIR (IST, Lisboa, Portugal) Michelangelo SCALE (F. Hoffmann-La Roche AG) Valerio ZATTI (University of Bologna, Italy) Scientific Committee Antonella DALLA CRT (President of GIC) Roberto GBETT (President of Inorg. Chem. Division SCI) Claudio PETTIARI (ISC Chair) Silvia BRDI Emanuela LICADR Alceo MACCHII Enrico MARCATI Alessandro MRDII Fabio RAGAII
6 SPEAKERS Martin Albrecht University College Dublin, Ireland Strong donor carbenes and their potential in (oxidation) catalysis Victorio Cadierno Menéndez Universidad de viedo, Spain Metal-catalyzed amide bond forming reactions in water: itrile hydrations and beyond Jonathan Clayden ew reactivity from organolithiums University of Manchester, United Kingdom dile Eisenstein University of Montpellier 2, France lefin metathesis catalysis with d0 Schrock metal alkylidene complexes: the input from computational studies A. Stephen K. Hashmi University of Heidelberg, Germany Gold catalysis - A universe of innovation David Milstein Sustainable catalysis based on pincer complexes Weizmann Institute of Science, Israel Carmen ajera Domingo Universidad de Alicante, Spain Coinage metal complexes as chiral catalysts for 1,3-dipolar cycloadditions
7 SPEAKERS Pedro J. Peréz Universidad de Huelva, Spain Catalytic Functionalization of Hydrocarbons: the Methane Problem Alessandra E. Quadrelli CPE Lyon, France Dinitrogen hydrogenation & cleavage an route to H 3 with a surface coordination chemistry perspective Gianna Reginato CR- ICCM Firenze, Italy Recent advances in cross coupling reactions. Synthetic applications in the field of new generation solar cells Francesco Ruffo University of apoli, Italy Sweetness and privilege of metal promoted asymmetric catalysis Peter Sadler University of Warwick, United Kingdom rganometallic anticancer complexes with new mechanisms of action Emmanuelle Shulz Université Paris-Sud 11, France Hydroamination reactions of unactivated olefins Kazuyuki Tatsumi University of agoya, Japan rganometallic chemistry of reductases - A clue to building a future sustainable society
8 LECTURES Friday, 30 August, h 16,00 Lecture 1 rganometallic Chemistry of Reductases: A Clue to Buildinga Future Sustainable Society Kazuyuki Tatsumi Research Center for Materials Science, agoya University, Furo-cho, Chikusa-ku, agoya , Japan Metalloenzymes are essential for all living organisms on earth, as their metal-incorporating active centers play a major role in regulating highly efficient/selective enzymatic functions. In particular, the research on reductases and related metalloenzymes has progressed rapidly in recent years, unraveling novel structures and functions of the cluster active centers and greatly expanding the established knowledge of chemistry. ewly discovered reductases show remarkable activities, exemplified by nitrogenases catalyzing the reduction of dinitrogen into ammonia, hydrogenases reversibly converting dihydrogen into protons and electrons, C-dehydrogenases generating protons and electrons from C and water, and acetyl CoA synthase forming acetyl CoA from carbon monoxide, methyl cobalamin, and coenzyme A (CoA). The brilliant functions of these enzymes stand out as a microcosm of the the mystery of nature that modern science should strive to understand, and therefore the importance of chemical research on the structure-function relationship of the active sites has been recognized. Friday, 30 August, h 18,00 Lecture 2 Computational studies and chemical complexity: olefin metathesis catalysis with the Schrock alkylidene complexes. dile Eisenstein Institut Charles Gerhardt, cc 1501, CRS UMR 5253, Université Montpellier 2, Place E. Bataillon, Montpellier, France Computational studies of reaction mechanism have gained increased visibility and credibility among the community of experimental chemists. It is currently accepted that a reaction mechanism can be determined by computational studies and the large number of mechanistic information obtained by computations, that has been useful to chemists is a daily proof of this success. How to conduct a study and give insight on a reaction knowing that the modeling could be far (even very far) from the experimental system and conditions? We will illustrate several points of the above by describing our work for the olefin metathesis reaction with the Schrock type metal alkylidene catalysts of the type d 0 M(=CHR)(ER1)(X)(Y) (M = Mo, W, Re; ER 1 = CR 1, R1, ; X = Y = alkyl, alloxy, siloxy, amido, etc. In this presentation, we will stress the importance of the chemical model (simplified vs closer to the experimental situation), the need to take a global vision of the reaction by including the study of the reactive pathway and that of the side reactions that form by products and could deactivate the catalyst. We will show that the classical Chauvin mechanism holds but needs to be completed. Some of the experiments were carried out with catalysts grafted on amorphous silica for which solid state MR is a method of choice. ne of the advantages of solid state MR is to access the dynamics of the catalysts grafted on silica via the measure of the Chemical Shift Anisotropy (CSA) for 13 C of the alkylidene group. Mo, W, Re and Ta alkylidene complexes were considered. The decrease of the CSA relative to a static limit suggests that the Mo complexes are essentially immobile, while the three others are relatively mobiles. A computational study of the time average CSA was carried out via a dynamic ab initio calculations of the systems grafted on silica. The methodology will be explained and the dynamics discussed. Remarkably, equal values of the CSA do not mean that the dynamics are of the same nature. The different dynamics will be presented and discussed. The Cluster Active Sites and Functions of Reductases These reductases promote organometallic reactions in nature. For instance, the function of C-dehydrogenases is equivalent to the so-called water-gas-shift reaction in organometallic chemistry, and acetyl CoA synthase involves the C insertion into a i-ch 3 bond in its function. Interestingly hydrogenases contain a typical organometallic iron-carbonyls in their active centers. The active sites of reductases are made of unprecedented transition metal sulfide clusters, which have been long-standing targets of synthetic chemists and are extremely challenging due to the instability and complexity of the cluster structures. This presentation shows our recent study on (1) chemical synthesis of the nitrogenase active sites and their electronic properties, (2) chemical synthesis of the [ife]-hydrogenase active sites and the model reactions, and (3) chemical synthesis of the active site of acetyl CoA synthase and the functional model. The first part will be based on the following papers and unpublished results. The computation studies of the CSA is still unpublished. rganometallics 2005, 24, J. Am. Chem. Soc. 2005, 127, rganometallics 2005, 24, ew J. Chem. 2006, 842. Dalton Trans. 2006, rganometallics 2006, 25, J. Am. Chem. Soc. 2007, 129, J. Am. Chem. Soc. 2007, 129, J. Am. Chem. Soc. 2008, 130, J. Am. Chem. Soc. 2010, 132, rganometallics 2012, 31, 6812.
9 Saturday, 31 August, h 9,00 Lecture 3 rganometallic anticancer complexes with new mechanisms of action Peter J. Sadler Department of Chemistry, University of Warwick, Coventry CV4 7AL, UK The periodic table offers potential for discovery of new drugs. 1 I will discuss our work on the design of low-spin d 6 halfsandwich organometallic Ru II, s II and and Ir III complexes. 2 Initially we synthesised monofunctional Ru II arene complexes that could bind strongly to DA, by guanine 7 coordination, H-bonding and intercalation of extended arenes, causing different structural perturbations to cisplatin and no cross-resistance. 3,4 However, it has become apparent that redox activity can play a role in activity. 5 For example, thiolato complexes can be activated by oxidation to the sulfenate, 6 and active inert complexes with strong π-acceptor chelated ligands can induce formation of reactive oxygen species (RS) in cancer cells. 7 The s II azopyridine complex [s(η 6 -p-cym)(4-(2-pyridylazo)-,-dimethylaniline)i]pf 6 exhibits nanomolar potency in a range of cancer cells and is active in vivo. 8 As for Ru II, the iodido and chlorido s II analogues exhibit marked differences in biological behaviour. 9 Compared to Ru II, s II arene complexes hydrolyse ca. 100x more slowly and an aqua ligand is ca. 1.5 pk a units more acidic. 2 Cyclopentadienyl Ir III complexes with appropriate Cp* substituents and chelated, or C, ligands 10 also possess some remarkable properties: potent anticancer activity 11 and catalytic activity using coenzyme ADH as a source of hydride under biologically-relevant conditions. 12,13 rganometallic arene complexes also offer potential for cancer photochemotherapy. 14 Acknowledgements: We thank the ERC, EPSRC, Science City (AWM/ERDF) and EC CST action CM1105 for support. Saturday, 31 August, h 11,00 Lecture 4 Dinitrogen hydrogenation & cleavage en route to H 3 with a surface coordination chemistry perspective: Elsje Alessandra Quadrelli Equipe Chimie rganométallique de surface, Laboratoire de Chimie Catalyse Polymères et Procédés (UMR 5265 C2P2 CPE Lyon CRS Univ. Lyon 1), Université de Lyon, 43, Bd du 11 ovembre Villeurbanne, Dinitrogen cleavage and hydrogenation by transition-metal centers toward ammonia is central in industry and in ature. After an introductory section on the thermodynamic and kinetic challenges linked to 2 splitting, this course discusses three major classes of transition-metal systems (homogeneous, heterogeneous and biological) capable of achieving dissociation and hydrogenation of dinitrogen. Molecular complexes, solid-state Haber-Bosch catalytic systems, silicasupported tantalum hydrides and nitrogenase will be discussed. Emphasis is focused on the reaction mechanisms operating in the process of dissociation and hydrogenation of dinitrogen. Close analysis of the mechanisms at hand in homogeneous, heterogeneous and enzymatic systems reveal the key role played by metal hydride bonds and metal-mediated bifunctional dihydrogen heterolytic splitting in elementary steps equivalent to electron and proton transfers. H + e - H + 2 e - [1] Barry,.P.E.; Sadler, P.J. Chem. Commun. 2013, 49, [2] offke, A.L.; Habtemariam, A.; Pizarro, A.M.; Sadler, P.J. Chem. Commun. 2012, 48, H + [3] Habtemariam, A.; Melchart, M.; Fernández, R.; Parsons, S.; swald, I.D.H.; Parkin, A.; Fabbiani, F.P.A.; Davidson, J.E.; Dawson, A.; Aird, R.E.; Jodrell, D.I.; Sadler, P.J. J. Med. Chem. 2006, 49, [4] Liu, H.-K.; Parkinson, J.A.; Bella, J.; Wang, F.; Sadler, P.J. Chem. Sci. 2010, 1, [5] Romero-Canelón, I.; Sadler, P.J. Inorg. Chem. 2013, in press. [6] Wang, F.; Xu, J.; Wu, K.; Weidt, S.K.; Mackay, C.L.; Langridge-Smith, P.R.; Sadler, P.J. Dalton Trans. 2013, 42, [7] Dougan, S.J.; Habtemariam, A.; McHale, S. E.; Parsons S.; Sadler, P.J. Proc. atl. Acad. Sci. USA 2008, 105, [8] Shnyder, S.D.; Fu, Y.; Habtemariam, A.; van Rijt, S.H.; Cooper, P.A.; Loadman, P.M.; Sadler, P.J. MedChemComm 2011, 2, 666. H H H H H [9] Romero-Canelón, I.; Salassa, L.; Sadler, P.J. J. Med. Chem. 2013, 56, [10] Liu, Z.; Habtemariam, A.; Pizarro, A.; Fletcher, S.; Kisova, A.; Vrana,.; Salassa, L.; Bruijnincx, P.; Clarkson, G.; Brabec, V.; Sadler, P.J. J. Med. Chem. 2011, 54, [11] Hearn, J.; Romero-Canelón, I.; Qamar, B.; Liu, Z.; Hands-Portman, I.; Sadler, P.J. ACS Chem. Biol. 2013, 8, [12] Betanzos-Lara, S.; Liu, Z.; Pizarro, A.M.; Qamar, B.; Habtemariam, A.; Sadler, P.J. Angew. Chem. Int. Ed. 2012, 51, [13] Liu, Z.; Deeth, R.J.; Butler, J.S.; Habtemariam, A.; ewton, M.E.; Sadler, P.J. Angew. Chem. Int. Ed. 2013, 52, [14] Barragán, F.; López-Senín, P.; Salassa, L.; Betanzos-Lara, S.; Habtemariam, A.; Moreno, V.; Sadler, P.J.; Marchán, V. J. Am. Chem. Soc. 2011, 133, LECTURES
10 LECTURES LECTURES Saturday, 31 August, h 14,30 Lecture 5 Coinage Metal Complexes as Chiral Catalysts for 1,3-Dipolar Cycloadditions Carmen ájera Domingo Department of rganic Chemistry, and rganic Synthesis Institute, University of Alicante, Apdo. 99, E Alicante, Spain, Saturday, 31 August, h 16,30 Lecture 6 Hydroamination reactions of unactivated olefins Emmanuelle Schulz Equipe de Catalyse Moléculaire, Institut de Chimie Moléculaire et des Matériaux d rsay, Université Paris Sud UMR 8182 rsay, France, The use of different chiral catalysts derived from binap and phosphoramidites and silver, gold(i) and copper(ii) salts for the enantioselective synthesis of highly substituted prolines by 1,3-dipolar cycloadditons (1,3-DC) of azomethine ylides, derived from imino esteres or azlactones, with dipolarophiles is presented. The 1,3-DC using bidentate binap complexes give good enantioselectivities for azomethine ylides when silver salts monomeric complexes 1, 1 and dimeric gold 2 trifluoroacetates 2 are used yielding endo-cycloadducts. Glycine derived azlactones react with maleimides using (S)- or (R)- dimeric binapautfa complexes 2 affording the corresponding endo-cycloadducts in good yields and high enantioselections, whereas, silver catalyst 1 failed completely. 3 The intermediate carboxylic acids are treated with trimethylsilyldiazomethane isolating 1 -pyrroline methyl esters as final products. In the case of monodentate phosphoramidites, metal complexes 3 derived from silver salts have been used for the general 1,3-DC of different imino esters and dipolarophiles to afford endo-cycloadducts. 4 In the case of using nitroalkenes as dipolarophiles copper(ii) triflate complexes 3 are the most appropriate catalysts affording exo-cycloadducts. 5 In addition, computational studies have also been carried out in order to explain the high enantioselection exhibited by these chiral complexes. This methodology has been applied to the synthesis of hepatitis C virus inhibitors blocking the viral RA-dependent RA-polymerase 6 and for the preparation of 4-nitroprolines, which are excellent chiral organocatalysts for the aldol reaction. 7 The metal-catalysed hydroamination of olefins, formally the addition of a H unit on an unsaturated carbon-carbon bond, perfectly meets the criteria of atom economic reaction. 1 The fine tuning of catalysts to perform this transformation with high enantioselectivities remains at present a real challenge to take up, considering the importance of these compounds in medicinal and natural products chemistry. This transformation is thermodynamically feasible under standard conditions but nevertheless suffers from a high activation barrier. lefinic activation through catalyst coordination is thus required to diminish the electron density or σ -H bond activation to increase the nucleophilicity. The last 60 years have seen a huge development of this reaction and numerous catalysts have been reported belonging to alkali bases, but also to the class of alkaline earth metals, rare-earth (actinides), group 4 (and 5) elements, late transition metals and organocatalysts. Recent efforts have been drawn towards the discovery of catalysts able to promote the reaction in an enantioselective manner. This lecture will give an overview about the development of hydroamination reactions, associated with the optimization of already known promoters or the emergence of new catalysts type. It is organized according to the type of catalyst engaged in the reaction and aims specifically to highlight the most innovative processes for the asymmetric hydroamination of unactivated alkenes, implying either an inter- or an intramolecular pathway. ur contribution in this field will also be [1] ájera, C.; de Gracia Retamosa, M.; Sansano, J. M. rg. Lett. 2007, 9, [2] Martín-Rodríguez, M.; ájera, C.; Sansano, J. M.; de Cózar, A.; Cossío, F. P. Chem. Eur. J. 2011, 17, [3] Martín-Rodríguez, M.; ájera, C.; Sansano, J. M. Synlett 2012, 62. [4] ájera, C.; de Gracia Retamosa, M.; Sansano, J. M. Angew. Chem. Int. Ed. 2008, 47, [5] Castelló, L. M.; ájera, C.; Sansano, J. M.; Larrañaga,.; de Cózar, A.; Cossío, F. P. rg. Lett. 2013, 15, (DI: /ol ) [6] Martín-Rodríguez, M.; ájera, C.; Sansano, J. M.; de Cózar, A.; Cossío, F. P. Beilstein J. rg. Chem. 2011, 7, 988. [7] This work has been supported by the DGES of the Spanish Ministerio de Ciencia e Innovación (MICI) (Consolider IGEI 2010 CSD and CTQ ), FEDER, Generalitat Valenciana (PRMETE/ 2009/039), and by the University of Alicante. presented, concerning the discovery of different new families of efficient lanthanide amide ate complexes based on the binaphthylamido ligand 2 or corresponding simple lithium salts 3 that promoted various hydroamination reactions. [1] Müller, E.; Hultzsch, K.C.; Yus, M.; Foubelo, F.; Tada, T. Chem. Rev. 2008, 108, Aillaud, I.; Collin, J.; Hannedouche, J.; Schulz, E. Dalton Trans. 2007, Hannedouche, J.; Schulz, E. Chem. Eur J. 2013, 19, [2] Hannedouche, J.; Aillaud, I.; Collin, J.; Schulz, E.; Trifonov, A. Chem. Commun. 2008, Chapurina, Y.; Hannedouche, J.; Collin, J.; Guillot, R.; Schulz, E.; Trifonov, A. Chem. Commun. 2010, 46, Chapurina, Y.; Guillot, R.; Lyubov, D.; Trifonov, A.; Hannedouche, J.; Schulz, E. Dalton Trans. 2013, 42, 507. [3] Deschamp, J.; lier, C.; Schulz, E.; Guillot, R.; Hannedouche, J.; Collin, J. Adv. Synth. Catal. 2010, 352, 2171.
11 Sunday, 1 September, h 8,30 Lecture 7 Sustainable catalysis based on cooperative pincer complexes David Milstein Department of rganic Chemistry, The Weizmann Institute of Science, Rehovot 76100, Israel Sunday, 1 September, h 10,00 Lecture 8 Strong donor carbenes and their potential in (oxidation) catalysis Martin Albrecht School of Chemistry & Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland In recent years, complexes based on cooperating ligands have exhibited remarkable catalytic activity. These ligands can cooperate with the metal center by undergoing reversible structural changes in the processes of substrate activation and product formation. Selected examples will be presented. ur group has discovered a new mode of metal-ligand cooperation, involving aromatization dearomatization of ligands. Pincer-type, pyridine- and bipyridine- based complexes of Ir, Rh, Ru, Fe, Pd, Pt and acridine complexes of Ru exhibit such cooperation, leading to facile activation of C-H, H-H, -H, -H bonds, and to novel, environmentally benign Ru-catalyzed reactions including (a) dehydrogenative coupling of alcohols to form esters and H 2 (b) hydrogenation of esters to alcohols under mild conditions (c) coupling of amines with alcohols to form amides, polyamides and peptides with liberation of H 2 (d) selective synthesis of primary amines directly from alcohols and ammonia (e) direct formation of acetals by dehydrogenative coupling of alcohols (f) generation of imines and hydrogen by coupling of alcohols with amines (g) dehydrogenative amidation of esters (h) dehydrogenative acylation of alcohols with esters (i) hydrogenation of amides to amines and alcohols (j) mild iron-catalyzed hydrogenation of ketones to alcohols (k) iron catalyzed C 2 hydrogenation to formate salts (l) hydrogenation of C 2-derived organic carbonates, carbamates, ureas and formates as alternative routes for the conversion of C 2 to methanol (m) catalytic transformation of alcohols to carboxylic acid salts using water as the terminal oxidant (n) synthesis of substituted pyrroles by dehydrogenative coupling of -amino-alcohols and secondary alcohols (o) synthesis of substituted pyridines by dehydrogenative coupling of -amino-alcohols and secondary alcohols. In addition, we have prepared Fe pincer complexes which exhibit high catalytic activity in hydrogenation of ketones and C 2. Very recently we have observed a new mode of activation of C 2 and nitriles by metalligand cooperation. Moreover, metal-ligand cooperation of this type has led to a distinct stepwise approach towards water splitting, based on consecutive thermal H 2 generation and light-induced 2 liberation, involving a new - bond-forming step. A powerful bond activation strategy relies on oxidative addition of (rather inert) bonds to electron rich transition metal centers. bviously, the effectiveness of this approach is greatly supported by strongly donating ligands. While phosphinebased ligands have been ubiquitous as strong donors for a wide variety of transition metal-catalyzed reactions, more recently -heterocyclic carbenes have gained in relevance as potent spectator ligands. Typically, -heterocyclic carbenes are associated with a largely covalent bonding and strong -donor properties, which distinguish them from phosphines. We will discuss the basic impact of -heterocyclic carbenes, and in particular synthetic opportunities for further increasing the donor ability of this type of ligand (see Figure below). 1 The lecture will focus specifically on understanding the reactivity and the catalytic activity of such strong donor systems compared to classical Arduengo-type HC complexes, in particular in redox-type transformations such as direct hydrogenation, transfer hydrogenation with high-valent transition metals, and water oxidation (see Fig right). 2 We will further discuss the scope and limitations of these strong donor carbene ligands, which includes non-innocent behavior and dissociative reactivities. 3 [1] For reviews: Albrecht, M. Chem. Commun. 2008, Schuster,.; Yang, L.; Raubenheimer, H. G.; Albrecht, M. Chem. Rev. 2009, 109, Donnelly, K. F.; Petronilho, A.; Albrecht, M. Chem. Commun. 2013, 49, [2] Selected examples from our laboratories: Lalrempuia, R. et al, Angew. Chem. Int. Ed. 2010, 49, 9765; Krüger, A. et al., Chem. Eur. J. 2012, 18, 652; Prades, A. et al. rganometallics 2011, 30, Petronilho, A. Dalton Trans. 2012, 41, [3] Krüger, A. et al. Aust. J. Chem. 2011, 64, Canseco, D.; lguin, J. submitted. LECTURES
12 LECTURES Sunday, 1 September, h 12,00 Lecture 9 ew Reactivity from rganolithiums Jonathan Clayden School of Chemistry, University of Manchester, xford Road, Manchester M13 9PL, UK rganolithiums are probably the most widely used organometallics in organic synthesis. From the handful of commercially available organolithiums, a wide range of functionalized organolithiums may be made by regioselective deprotonation, halogen-metal exchange, transmetallation or carbolithiation. The lecture will start with an overview of these methods and will outline some general rules for making effective use of directing effects to construct target molecules effectively. It will stress the importance of solvation and intramolecular coordination effects, as well as stereoelectronic effects, in these regioselective reactions. Stereoselective features may be introduced by the use of chiral ligands, especially the alkaloid ( )-sparteine and its analogues. The lecture will cover the most useful of these methods, and outline the detailed mechanisms by which asymmetry may be induced in RLi ( )-sparteine directed reactions. Examples of target-directed syntheses based around this chemistry will be given. pportunities for catalysis with organolithiums are currently relatively limited, and the state of the art in this area will be described. Typically, simple organolithiums are used as bases, and more complex organolithiums are used as nucleophiles, with classical nucleophile-electrophile couplings dominating their practical utility. However, more recent work has uncovered some remarkable alternative reactivity patterns that are available to organolithiums under certain conditions of solvation or in certain conformations. These include dearomatising nucleophilic attack on aromatic rings and aryl migration reactions. Effectively, these reactions widen considerably the scope of classical nucleophilic aromatic substitution chemistry to include not only electron-deficient but also electron-rich coupling partners. These organolithium reactions thus provide an alternative, mechanistically unique way to make new C C bonds, particularly at hindered positions. They allow the construction of unusual or otherwise difficult to obtain structural features in target molecules, and examples of such syntheses will be described. rganolithium chemistry is relatively easy to understand in terms of a few mechanistic principles, and recently the application of tools such as in situ IR spectroscopy (React-IR) has uncovered previously hidden detail in their chemistry. These advances will be briefly described. Background information is provided in rganolithiums: Selectivity for Synthesis, Clayden, J. Pergamon, 2002 and in Dearomatizing reactions using organolithiums Lemière, G. and Clayden, J. Science of Synthesis, Knowledge Updates 2011, 4, For leading recent references, see: Amines bearing tertiary substituents by tandem enantioselective carbolithiation- rearrangement of vinyl ureas Tait, M.; Donnard, M.; Minassi, A.; Lefranc, J.; Bechi, B.; Carbone, G.; Brien, P.; Clayden, J. rg. Lett. 2013, 15, 34-36; Intramolecular vinylation of secondary and tertiary organolithiums Lefranc, J.; Fournier, A. M.; Mingat,G.; Herbert, S.; Marcelli, T.; Clayden, J. J. Am. Chem. Soc. 2012, 134, ; A general synthetic approach to the amnesic shellfish toxins: total synthesis of ( )-isodomoic acid B, ( )-isodomoic acid E, and ( )-isodomoic acid F Lemière, G.; Sedehizadeh, S.; Toueg, J.; Fleary-Roberts,.; Clayden, J. Chem. Commun. 2011, Monday, 2 September, h 9,30 Lecture 10 Catalytic Functionalization of Hydrocarbons: the Methane Problem Pedro J. Pérez Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQS-Centro de Investigación en Química Sostenible and Departamento de Química y Ciencia de los Materiales, Universidad de Huelva, Campus de El Carmen Huelva, Spain Methane is available in the earth crust either in natural gas (80-90%) or in shale gas (up to 98%), a fact that could make it as an ideal raw material for C1 chemistry. However, the main use of methane from an industrial point of view is restricted to the generation of syngas, further employed in the synthesis of methanol, in the Fischer-Tropsch process or in carbonylation/hydrogenation reactions. Examples of the direct functionalization of methane are yet scarce and in all cases confined to the lab scale. 1 We have recently reported 2 the catalytic functionalization of methane using silver-based catalysts that induce the insertion of carbene units CHC 2Et from ethyl diazoacetate to the C-H bond of methane through transient silver-carbene intermediates. A family of fluorinated silver catalysts has been developed to promote this transformation, that takes place in sc-c 2 as the reaction medium. Competition experiments with the C 1-C 4 alkane series have provided the values of the relative reactivity of the C-H bonds of the light alkanes, from which interesting information regarding the mechanism of this transformation have been obtained. [1] Alkane C-H Activation by Single-Site Metal Catalysis, Pérez, P. J. Ed. Springer, 2012, Dordrecht. 14% 30% 56% 53% [2] Caballero, A.; Despagnet-Ayoub, E.; Díaz-Requejo, M. M.; Díaz-Rodríguez, A.; González-úñez, M. E.; Mello, R.; Muñoz, B. K.; Solo jo, W.; Asensio, G.; Etienne, M.; Pérez, P. J. Science 2011, 332, ry:2ry 1 : ry:2ry 1 : 2.65
13 Monday, 2 September, h 11,30 Lecture 11 Sweetness and privilege of metal promoted asymmetric catalysis Francesco Ruffo Dipartimento di Scienze Chimiche, Università di apoli Federico II, apoli, Italy, and Consorzio Interuniversitario di Reattività Chimica e Catalisi, Italy, It is nowadays acknowledged the importance of developing convenient methodologies to produce enantiomerically pure products. 1 Within this context, asymmetric organometallic catalysis is one of the most successful strategies. Since the first examples dated 1966, 2 organometallic catalysts have attracted increasing interest in both academic and industrial contexts, for some clear advantages: (i) the remarkable activity, which allows the use of high substrate/metal ratios; (ii) the tunability of the coordination environment, that widens the scope of substrates; (iii) the tolerance to functional groups, which enhances chemoselectivity, and then simplifies the purification of the products. (iv) the flexibility of the physical properties, which helps separation and recycle of the catalyst. 3 bjective of this lecture is to provide the essential tools for addressing asymmetric organometallic catalysis. It is first explained the value of this methodological approach, through a brief historical introduction. A careful evaluation of the leading actors follows, with the description of the role of the metal (the activating agent), the substrate (from pupa to butterfly) and the chiral ligand (the conductor). Then, the research activities 4 of the organometallic chemistry group in apoli are briefly presented. Monday, 2 September, h 15,00 Lecture 12 Gold catalysis - A universe of innovation A. Stephen K. Hashmi Ruprecht-Karls Universität Heidelberg, rganisch-chemisches Institut, Im euenheimer Feld 270, Heidelberg, Germany In the last decade homogenous gold catalysis has developed into a powerful tool for organic synthesis. 1] In this highly active field the use of diynes as substrates has only recently been explored. Here new cyclisation modes of 1,2-diynearenes to undergo selective intramolecular and intermolecular C-H activation of unactivated C-H bonds are reported (). 2-4 The mechanism of this transformation involves two gold centers (principle of dual activation ), both synergistically activating the substrates for cyclisation via - and σ-coordination. A bifurcation on the potential energy surface gives access to gold-vinylidenes or gold-carbenes, both highly reactive intermediates capable for C-H activation. 5 Depending on the backbone of the diyne system, a change on the bifurcation energy surface to selectively lead to gold vinylidenes or gold carbenes. Both intermediates are highly interesting as they represent a new class of organogold compounds and offer new perspectives for homogenous gold catalysis. LECTURE [1] (a) oyori, R. Angew. Chem. Int. Ed. Engl., 2013, 52, 79; (b) Asymmetric Catalysis on Industrial Scale (Eds. Blaser, H.U.; Schmidt, E.), Wiley-VCH, Weinheim, [2] (a) ozaki, H.; Moriuti, S.; Takaya, H.; oyori, R. Tetrahedron Lett., 1966, 5239; (b) Knowles, W.S.; Sabacki, M.J. Chem. Commun., 1968, [3] Multiphase Homogeneous Catalysis (Eds. Cornils, B.; Herrmann, W.A.; Horvath, I.T.; Leitner, W.; Mecking, S.; livier-borbigou, H.; Vogt, D.), Wiley-VCH, Weinheim, [4] Lega, M.; Figliolia, R.; Moberg, C.; Ruffo, F. Tetrahedron, 2013, 69, 4061, and refs therein. A universe of dual-gold catalyzed cyclizations of diynes [1] Rudolph, M. ; Hashmi, A. S. K. Chem. Soc. Rev. 2012, 41, [2] Hashmi, A. S. K.; Braun, I; Rudolph, M.; Rominger F. rganometallics 2012, 31, [3] Hashmi, A. S. K.; Braun, I.; ösel, P.; Schädlich, J.; Wieteck, M.; Rudolph, M; Rominger, F. Angew. Chem. Int. Ed. 2012, 51, [4] Hashmi, A. S. K; Wieteck, M.; Braun, I.; Rudolph, M.; Rominger, F Angew. Chem. Int. Ed. 2012, 51, [5] Hansmann, M. M.; Rudolph, M.; Rominger, F.; Hashmi, A. S. K. Angew. Chem. Int. Ed. 2013, 52, LECTURES
14 LECTURES Tuesday, 3 September, h 9,00 Lecture 13 Metal-catalyzed amide bond forming reactions in water: itrile hydrations and beyond Victorio Cadierno Menéndez Laboratorio de Compuestos rganometálicos y Catálisis (Unidad Asociada al CSIC), Departamento de Química rgánica e Inorgánica, Universidad de viedo, Julián Clavería 8, viedo, Spain. Amides are versatile building blocks in synthetic organic chemistry, present a wide range of pharmacological applications, and are used as raw materials in industry for the large-scale production of engineering plastics, detergents and lubricants. The development of green procedures for the synthesis of this relevant class of compounds is therefore of prime interest in modern chemistry. In the search of improved synthetic methods, metal-catalyzed transformations have emerged in recent years as the most promising alternatives for the atom-economical and cost effective synthesis of amides, opening also previously unavailable routes that start from substrates other than carboxylic acids and their derivatives. In this lecture, a brief overview of metal-catalyzed synthetic approaches of amides conducted in environmentally friendly aqueous media will be presented. 1 Subsequently, the work of our group on the development of hydrophilic ruthenium catalysts for nitrile hydration reactions in water, 2 and related amide bond forming reactions starting from aldoximes and aldehydes, 3 will be discussed in depth. Tuesday, 3 September, h 10,30 Lecture 14 Recent advances in cross-coupling reactions. Synthetic applications in the field of new generation solar cells Gianna Reginato CR-ICCM Istituto di Chimica dei Composti rganometallici, Via madonna del Piano 10, Sesto Fiorentino (FI), Italy, Transition metal-catalyzed cross-coupling reactions between organic halides and organo-metallic reagents constitute one of the most straightforward methods for the formation of carbon carbon bonds. 1 This has been recognized in 2010 by the awarding of the obel prize in chemistry to Richard Heck, Ei-ichi egishi, and Akira Suzuki for palladium-catalyzed cross-couplings in organic synthesis. Indeed, numerous examples of such process have been developed and exploited as a powerful tool to assemble complex molecular frameworks of a range of interests encompassing total synthesis of natural products 2, medicinal chemistry, industrial process development 3 as well as chemical biology, materials, and nanotechnology. Such an important reaction can be described by the simple equation reported in the following scheme, were R and R are organic groups, X is an halogen atom or a related heteroatom leaving group, m is the metal countercation of the organometallic species involved and M is a transition metal. [1] For a recent review on this topic, see: García-Álvarez, R.; Crochet, P.; Cadierno V. Green Chem. 2013, 15, 46. [2] Cadierno, V.; Francos, J.; Gimeno, J. Chem. Eur. J. 2008, 14, 6601; Cadierno, V.; Díez, J.; Francos, J.; Gimeno, J. Chem. Eur. J. 2010, 16, 9808; García-Álvarez, R.; Díez, J.; Crochet, P.; Cadierno, V. rganometallics 2010, 29, 3955; García-Álvarez, R.; Francos, J.; Crochet, P.; Cadierno, V. Tetrahedron Lett. 2011, 52, 4218; García-Garrido, S. E.; Francos, J.; Cadierno, V.; Basset, J.-M.; Polshettiwar, V. ChemSusChem 2011, 4, 104; García-Álvarez, R.; Díez, J.; Crochet, P.; Cadierno, V. rganometallics 2011, 30, 5442; García-Álvarez, R.; García-Garrido, S. E.; Díez, J.; Crochet, P.; Cadierno, V. Eur. J. Inorg. Chem. 2012, [3] García-Álvarez, R.; Díaz-Álvarez, A. E.; Borge, J.; Crochet, P.; Cadierno, V. rganometallics 2012, 31, 6482; García-Álvarez, R.; Díaz- Álvarez, A. E.; Crochet, P.; Cadierno, V. RSC Adv. 2013, 3, Despite the simplicity of the process and the huge number of studies and very elegant and efficient examples which are present in the literature, research in this area is still very active. Particular attention is devoted to the development of new and more efficient catalytic systems, which might be able to activate less reactive substrates, to allow a better functional group tolerance, to make possible catalysts recycling. In addition, new environmentally benign reactions conditions aimed to replace expensive reagents, toxic and flammable organic solvents, high temperatures and long reaction times, have been investigated in order to facilitate the application of this methodology in industry. Among the others, cross-coupling reactions represents probably the most widely used method for aryl-aryl bond formation and, more in general, for the synthesis of highly conjugated polyenes and have found a very stimulating field of application in the molecular design of metal-free organic dyes for applications in DSSC 4, a new generation of photovoltaic devices which offer the possibility of low-cost conversion of solar energy. [1] Metal-Catalyzed Cross-Coupling Reactions; Meijiere, A. d., Diederich, F 2nd Completely Revised and Enlarged ed.; WILEY-VCH, 2004,Weinheim, Vol.1-2. [2] icolaou, K. C.; Bulger, P. G.; Sarlah, D. Angew. Chem. Int. Ed. 2005, 44, [3] C. Torborg and M. Beller, Adv. Synth. Catal., 2009, 351, 3027 [4] Mishra A.; Fischer, M.K.R.; Bäuerle P. Angew. Chem. Int. Ed. 2009, 48, 2474.
15 SPSRS
16 PSTERS Poster 1 Glucose-derived Bis(pyridine-2-carboxamide) Ligands for Molybdenum Catalyzed Asymmetric Allylic Alkylations Matteo Lega,* Francesco Ruffo Dipartimento di Scienze Chimiche, Università di apoli Federico II, Italy Consorzio Interuniversitario di Reattività Chimica e Catalisi, Italy, The elpa-py family of ligands 1 (Figure 1), which represents a subset of the elpa-type library based on D-glucose, 2 is described. The ligands are structural analogues of the privileged bis(pyridine-2-carboxamides) derived from trans-1,2-diaminocyclohexane, 3 and differ for the type of substitution in the coordinating functions present in positions 1 and 2. Their ability to induce high enantioselectivity in asymmetric allylic alkylations promoted by molybdenum under microwave irradiation has been successfully demonstrated (Figure 2), starting from both a linear (ee up to 99%) and a branched substrate Poster 2 Synthesis of rganometallic Assemblies from Quinonoid Zwitterions Minghui Yuan, a,b Bruno Therrien, a * Lucie Routaboul, b Pierre Braunstein b * a Institut de Chimie, Université de euchâtel, Avenue de Bellevaux 51, CH2000, Suisse, b Institut de Chimie (UMR 7177 CRS), Université de Strasbourg, 4 rue Blaise Pascal, Strasbourg Cedex, France Following our previous work on metalla-assemblies, 1 a large cationic triangular metalla-prism [Ru 6(pcymene) 6(tpt) 2(L) 3] 6+, incorporating (p-cymene) ruthenium building blocks, bridged by, -R,R-2-amino-5-alcoholate- 1,4-benzoquinonemonoiminium zwitterionic ligands (L), 2 and connected by two 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (tpt) subunits allows the encapsulation of various guest molecules. These cationic cages and cationic host-guest systems have been isolated as their triflate salts. The formation of the cages was confirmed by MR spectroscopy. The properties of these systems were studied in solution by acid-base titrations, allowing the determination of the ph needed to break the cages. Moreover, the solubility and property of the cages can be modified by introduction of different functional groups on the zwitterionic ligand y. (ee up to 96%). The multifunctional nature of the sugar scaffold was exploited for the preparation of a polar ligand, through deprotection of the hydroxyl groups in positions 3, 4 and 6. In this version, it was possible to verify the performance in catalysis in alternative solvents, such as ionic liquids and water. Figure 2 [1] Lega, M.; Figliolia, R.; Moberg, C.; Ruffo, F.;. Tetrahedron 2013, 69, [2] V. Benessere, A. De Roma, R. Del Litto, M. Lega, F. Ruffo; Eur. J. rg. Chem., 2011, 29, [3] Belda,.; Moberg, C. Acc. Chem. Res. 2004, 37, 159. [1] a) Therrien, B.; Süss-Fink, G.; Govindaswamy, P.; Renfrew, A.K.; Dyson, P.J. Angew. Chem. Int. Ed. 2008, 47, ; b) Mattsson, J.; Govindaswamy, P.; Furrer, J.; Sei, Y.; Yamaguchi, K.; Süss-Fink, G.; Therrien, B. rganometallics 2008, 27, [2] a) Siri,.; Braunstein, P. Chem. Commun, 2002, ; b) Yang, Q.Z.; Siri,.; Braunstein, P. Chem. Commun, 2005,
17 Poster 3 Electronic Effect in Iron Catalysed C-H Bond xidation Giorgio livo, a* svaldo Lanzalunga, a Luigi Mandolini, a Stefano Di Stefano, a a Sapienza Università di Roma, Dipartimento di Chimica, Piazzale Aldo Moro 5, Roma(RM), Italy, The search for efficient and selective methods to oxidize C-H bonds has been a longstanding goal in organic chemistry. However, it is less than 6 years that this goal managed to become a useful tool in synthetic chemists hands by the use of nonheme iron catalysts. ne of the most efficient catalytic systems prepared so far is White s complex, 1 reported in Figure 1 (R=H, the first structure on the left). With the aim at shedding some light on the mechanism by which this system works, we prepared the three substituted iron (II) PDP complexes shown below. The chosen substituents allow a wide investigation of the electronic effects on the catalytic efficiency of the system. The results obtained in the oxidation of C-H bonds of some non-activated hydrocarbons substrates will be shown together with the synthetic route and a full characterization of the new iron complexes. Poster 4 Synthesis and xygenation of Dialkylborane Complexes with Selected, -Bifunctional Ligands Anna B. Rola-oworyta, a * Michał Lesiuk, c Iwona Justyniak, a Janusz Lewiński a, b a Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, Warsaw, Poland, b Faculty of Chemistry, Warsaw University of Technology, oakowskiego 3, Warsaw, Poland, c Faculty of Chemistry, University of Warsaw, Pasteura 1, Warsaw, Poland, In the recent decades metaloorganic complexes of 13 th group elements were shown to catalyze various organic reactions. This type of complexes can also be used as precursors for formation of ceramic materials. In order to rationally design the catalysts and precisely control those reactions, it is important to understand factors controlling structure and reactivity of the molecular complexes. Especially, mechanism of oxygenation of those complexes is very interesting from practical point of view. Lewiński s group has been interested in the oxygenation reaction of the complexes for many years. Systematic investigations performed by our group show, that ligand used for complex formation greatly influences oxygenation mechanism and its products. Therefore, by careful selection of the ligand we may obtain valuable precursors or catalysts. To date most of the work has been concentrated on dialkylaluminum complexes. Much less is known about interaction of dialkyborane complexes with molecular oxygen. Et BEt 3 +,' H B + Et ' Et H Scheme 1 [1] Chen, M. S.; White M. C. Science 2007, 318, In the presented work, synthesis of dialkylborane complexes with selected, -ligands (Scheme 1) as well as characterization of their products by 1 H and 11 B MR, IR and X-ray diffraction will be discussed. To confirm proposed molecular structures of the complexes, experimental 11 B MR spectra were compared with results of quantum mechanics calculations at the DFT level. Those results confirm that the complexes exhibited both, tetra- and tri-coordinated structures depending on the used ligand. Subsequently, the synthesized compounds were oxygenated in order to elucidate mechanism of the dialkylborane complexes reaction with molecular oxygen. n the basis of 1 H MR results one can conclude that only the diethylborane complexes with methyl salicylate and methyl lactate easily undergo the oxidation. These results suggest that propensity of the alkylborane complex toward oxygenation is connected with the asymmetrical structure of ligand containing asymmetric side groups. ur attempts to correlate electrochemical oxidation potentials of the complexes with their tendency to reaction with molecular oxygen will also be discussed. PSTERS
18 PSTERS Poster 5 Synthesis and Characterization of Rhodium anoparticles Stabilized by Triphenylphosphine and Application in Catalytic Hydrogenation Mahmoud Ibrahim,* a,b Karine Philippot* a,b a CRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de arbonne, BP44099, F Toulouse Cedex 4, France; b Université de Toulouse, UPS, IPT, F Toulouse Cedex 4, France ; ver the last few decades the synthesis of monodisperse, size- and shape-controlled metal nanoparticles (Ps) has become one of the major goals in nanosciences. 1 Interest was shown toward these nano-sized particles since they form a class of materials with properties distinctly different from their bulk and molecular counterparts. 2 Consequently, metallic nanoparticles found numerous applications, notably in the field of catalysis. 3, 4 The decomposition of organometallic precursors under mild conditions showed to be a successful synthetic methodology to give well-controlled metallic nanoparticles displaying a very small size. 5 This is a key feature to achieve high catalytic activity due to high surface area of metallic atoms. 6 A stabilizing agent (coordinating ligands, 7 polymers, 1 etc.) is required to prevent the agglomeration of the metal nanoparticles. This stabilizer can also govern the surface chemistry of the Ps as allowing them to be soluble in water for example vii Poster 6 Microwave Assisted Synthesis of Shvo s Type Catalysts Cristiana Cesari,* Rita Mazzoni, Letizia Sambri, Valerio Zanotti Dipartimento di Chimica Industriale Toso Montanari, viale Risorgimento, Bologna Italy; Shvo s catalyst {[Ph 4(η 5 -C 4C)] 2H}-Ru 2(C) 4H has been applied successfully in a broad scope of hydrogen-transfer processes, 1 therefore development of new protocols for a fast and convenient synthesis of such derivatives is a current challenge. Here we report on a simple, environmentally friendly, expeditious microwave-assisted procedure for the synthesis of Shvo s type complexes through the reaction between Ru 3(C) 12 and variously functionalized tetraarylcyclopentadienones, which provides good yields and purities within 50 min at 110 C (Scheme 1). Scheme 1 Here in, we will present the synthesis of spherical, ultra small and monodisperse Rhodium nanoparticles synthesized from [Rh(C 3H 5) 3] precursor. The size of these Ps is controlled by a suitable quantity of triphenylphosphine as a stabilizing ligand. Full characterization in terms of morphology and surface state (solution 1 H MR and 13 P MR, solid state MR, IR-FT, TEM, HRTEM and EDX, WAXS analysis) for these Ps will be also presented. These systems were tested in hydrogenation reaction of model alkenes and arenes showing high activity under mild conditions. The reaction is general and leads to yields similar to the conventional refluxing method (ca. 70 %). By far, the most important outcome of this new method concerns the improvement in reaction time from 40 h in the conventional method to 50 min in our microvawe assisted one. Indeed functionalized catalysts maintain the catalytic activity and selectivity toward the reduction of aldehydes and ketones. [1] Conley, B. L.; Pennington-Boggio, M. K.; Boz, E.; Williams, T. J. Chem. Rev. 2010, 110, Busetto, L.; Fabbri, D.; Mazzoni, R.; Salmi, M.; Torri, C.; Zanotti, V. Fuel 2011, 90, [2] Casey, C. P.; Singer. S.; Powell, D. R.; Hayashi, R. K.; Kavana, M. J. Am. Chem. Soc., 2001, 123, 1090 [1] Tuchscherer, A.; Packheiser, R.; Rüffer, T.; Schletter, H.; Hietschold, M.; Lang, H.Eur. J. Inorg. Chem. 2012, 2251 [2] Moshfegh, A. Z. J. Phys. D: Appl. Phys. 2009, 42, [3] oël, S.; Léger, B.; Herbois, R.; Ponchel, A. ; Tilloy, S. ; Wenz, G.; Monflier, E. Dalton Trans. 2012, 41, [4]. Yan, C. Xiao and Y. Kou, Coord. Chem. Rev. 2010, 254, [5] Philippot, K.; Chaudret, B. C. R. Chim. 2003, 1019/Patricia, L.; Philippot, K.; Chaudret, B. ChemCatChem 2013, 5, 28 [6] Roucoux, A.; Philippot, K. Hydrogenation With oble Metal anoparticles in Handbook of Homogenous Hydrogenations; Wiley-VCH: Weinheim, [7] Debouttiére, P-J.; Martinez, V.; Philippot, K.; Chaudret, C. Dalton Trans. 2009,
19 Poster 7 Solid-State Characterization of MFs for Electroluminescent Applications F.Grifasi,* a M.R.Chierotti, a R. Gobetto, a D. Braga, b F. Grepioni, b L. Maini, b P. Pelagatti c a Department of Chemistry, Via Pietro Giuria 7, 10125, Turin, Italy; b Department of Chemistry G. Ciamician, Via Selmi 2, 40126, Bologna, Italy; c Department of Chemistry, Parco Area delle Scienze 17/A, 43100, Parma, Italy In this communication we report the synthesis and the characterization of different types of Metal-rganic-Framework (MF). MFs are a recently-identified class of porous material with a specific three-dimensional structure, consisting of metal ions linked together by organic bridging ligands. Their development represents a new approach on the interface between molecular coordination chemistry and materials science. 1 In fact, MFs are attracting considerable attention for applications such as gas storage, separations, catalysis, and also, in recent years, for their potential uses in electronic devices. 2 Their potentiality lies on several peculiar properties, such as large pore sizes, high surface areas, selective uptake of small molecules and optical or magnetic responses to the inclusion of guests. More importantly, their synthesis from molecular building blocks holds the potential for directed tailoring of these properties. 3 This work focuses on MFs based on copper iodide (CuI), cyanide (CuC) or thiocyanate (CuSC) with aza-ligands (DABC and di-anhydride perilenes) to be used as electroluminescent devices (static host-guest interaction processes). In particular, MFs synthesis have been carried out especially through a solid-state solvent-free approach (mechanochemical methods), but also through more traditional techniques such as solvothermal/hydrothermal synthesis and crystallization. The structural characterization on powder samples has been fulfilled through the following spectroscopic techniques: Solid-State uclear Magnetic Resonance (SS MR), RAMA and Infrared Spectroscopies, X-Ray Powder Diffraction (XRPD) and, when possible, Single Crystal X ray Diffraction. Concerning the SS MR analysis, samples characterization was performed through 13 C CP MAS to evaluate the ligands coordination, 15 CP MAS to investigate copper-nitrogen interactions, and 63 Cu spectra (Hahn-Echo sequence, Solid Echo sequence and Direct Exitation) to analyze metal sites. This represents a very important challenge because of the lack of data reported in literature about copper analysis by SS MR. Poster 8 ovel Water Soluble Symmetrical and on-symmetrical 11 th Group-HC Complexes: Synthesis, Citotoxicity and SAR Study Marika Marinelli,* a Maura Pellei, a Giancarlo Gioia Lobbia, a Cristina Marzano, b Valentina Gandin, b Alessandro Dolmella, b H. V. Rasika Dias c and Carlo Santini a a School of Science and Technology, Chemistry Division, University of Camerino, via S. Agostino 1, Camerino, Italy; b Department of Pharmaceutical and Pharmacological Sciences, University of Padova, via Marzolo 5, Padova, Italy; c Department of Chemistry and Biochemistry, The University of Texas at Arlington, Box 19065, Arlington, Texas , United States; As potential anticancer drugs, -Heterocyclic Carbene (HC) complexes constitute a recent and fruitful field of research. ur research group, during the last 5 years, has developed different classes of coinage metal-hc complexes obtained from the precursors {[HB(RImH) 3]Br 2} (R = Benzyl, Mesityl and t-butyl) 1, {[H 2B(BnTzH) 2]Br}, 2 {[H 2B(p 2BnTzH) 2]Br}, 3 {H 2C(HTz R ) 2} and {H 2C(HIm R ) 2} (HTz = 1,2,4-triazole; HIm = imidazole; R = (CH 2) 3S - 3 or (CH 2) 2C - ). 4 Recently we have focused the research work on the development of new coinage metal-hcs complexes obtained from the water soluble ligands Him 1R,3R Cl (R = CCH 3, CCH 2CH 3 or C(CH 2CH 3) 2) 5 or the zwitterionic water soluble precursor ahim 1R,3R (R = (CH 2) 3S - 3 ). 6 Here we report the synthesis of the novel zwitteronic symmetrical HC ligands ahim 1R,3R,4R (R = (CH 2) 3S - 3, R = H, CH 3 or 2) (), ahbzim 1R,3R (R = (CH 2) 3S - 3 ) and non-symmetrical HC ligands ahim 1R,3R,4R (R = (CH 2) 3S - 3, R = CH 2C 6H 5, R = H, CH 3 or 2), {[HBzim 1R,3R ]Br} (R = (CH 2) 3S 3a, R = CH 2C 6H 5) and the related silver(i)-hc complexes. 3 Finally we report the cytotoxic activity and the SAR study of the HC complex classes developed by our research group. [1] Stuart L.J. et al., Chemical Society Review, 2003, 32, [2] Allendorf M.D. et al., Chemical European Journal, 2011, 17, [3] Rowsell L.C. et al., Microporous and Mesoporous Materials, 2004, 73, rtep of ahim 1R,3R (R = (CH2)3S3 -, R = CH2C6H5,) [1] Biffis, A.; Gioia Lobbia, G.; Papini, G.; Pellei, M.; Santini, C.; Scattolin, E.; Tubaro, C., J. rganomet. Chem. 2008, 693, [2] Papini, G.; Bandoli, G.; Dolmella, A.; Gioia Lobbia. G.; Pellei, M.; Santini, C., Inorg. Chem. Commun. 2008, 11, [3] Marinelli, M., et al., unpublished results. [4] Papini, G.; Pellei, M.; Gioia Lobbia G.; Burini, A.; Santini, C., Dalton Trans. 2009, [5] Pellei, M.; Gandin, V.; Marinelli, M.; Marzano, C.; Yousufuddin, M.; Dias, H. V. R.; Santini, C., Inorg Chem 2012, 51, [6] Gandin, V.; Pellei, M.; Marinelli, M.; Marzano, C.; Dolmella, A.; Giorgetti, M; and Santini, C.; J. Inorg.Biochem., submitted PSTERS
20 PSTERS Poster 9 Synthesis of -Heterocyclic Dicarbenes Derived from Bis(pyrazol-1-yl)alkane Ligands Poster 10 ovel Copper and Silver Catalysts for Hydrocarbons Functionalization Andrei S. Potapov, * Lina V. Zatonskaya, Andrei I. Khlebnikov R. Gava,* a A. lmos, a A. Caballero, a,* G. Asensio, b,* P. J. Pérez a,* Department of Food and Chemical Industry, Altai State Technical University, 46 Lenin Ave Barnaul, Russia, Chemistry of stable -heterocyclic carbenes (HCs) is a rapidly developing area of organic and organometallic chemistry. Metal complexes of -heterocyclic carbenes often demonstrate high catalytic activity. 1 HCs based on imidazole derivatives are widely known, one of the most important example of their complexes is Grubbs olefin metathesis catalyst. 2 Carbenes based on other azoles, namely pyrazole and triazole are much less studied, 3 especially those containing two or more carbene centers. 4 Previously we have developed an efficient approach to bis(pyrazol-1-yl)alkane and related ligands by the reaction of azoles with dibromoderivatives in a superbasic KH-DMS system followed by pyrazole ring functionalization. 5 Here we report the synthesis of bis(pyrazolium) salts with long aliphatic spacers as precursors for the generation of pyrazole-derived dicarbenes (). a Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQS-Centro de Investigación en Química Sostenible y Departamento de Química y Ciencia de los Materiales, Universidad de Huelva Huelva, Spain; b Departamento de Química rgánica, Facultad de Farmacia, Universidad de Valencia, Burjassot Valencia, Spain; ne of the most interesting research areas is the development of effective processes for the functionalization of alkanes 1. Catalysis is an effective method for this goal but it is yet underdeveloped mainly due to the very high dissociation energy of the C-H bonds in these compounds. ur research group has developed a series of group 11 metal catalysts able to functionalize alkanes by carbene insertion from diazo compounds, 2 a methodology that has recently been applied to methane. 3 With the aim of improving the catalytic activity of this substrate as well as the primary positions of linear alkanes, novel Cu and Ag complexes with new scorpionate ligands have been being developed, their catalytic capabilities being presented herein. Acknowledgements: The reported study was supported by RFBR, research projects os and [1] Dıez-Gonzalez, S.; Marion,.; olan S. P. Chem. Rev. 2009, 109, [2] Scholl, M.; Trnka, T.M.; Morgan, J.P.; Grubbs R.H. Tetrahedron Lett. 1999, 40, [3] Schuster,.; Yang, L.; Raubenheimer, H. G.; Albrecht M. Chem. Rev. 2009, 109, [4] Han Y., Lee L.J., Huynh H.V. // Chem. Eur. J. 2010, 16, 771. [5] Potapov, A.S.; Domina, G.A.; Khlebnikov, A.I.; gorodnikov, V.D. Eur. J. rg. Chem. 2007, [1] Pérez, P. J. Alkane C-H Activation by Single-Site Metal Catalysis, Springer, Dordrecht, [2] Díaz-Requejo, M. M.; Pérez, P. J. Chem. Rev. 2008, 108, [3] Caballero, A.; Despagnet-Ayoub, E; Díaz-Requejo, M. M.; Díaz-Rodríguez, A.; González-úñez, M. E.; Mello, R.; Muñoz, B. K.; Solo jo, W.; Asensio, G; Etienne, M.; Pérez, P. J. Science, 2011, 332,
21 Poster 11 Fluoroalkyl Allyl Ethers: Useful Building Blocks for the Synthesis of Perfluorinated Molecules Dario Lazzari, a Maria Cristina Cassani, b Marta Brucka, b Gavino Solinas,* b Marisa Pretto a Poster 12 Direct syn Insertion of Alkynes and Allenes into Au-Si bonds Maximilian Joost,* a Pauline Gualco, a Sonia Mallet-Ladeira, b Laura Estevez, c Karinne Miqueu, c Abderrahmane Amgoune, a * Didier Bourissou a * a Miteni S.p.A, Località Colombara, 91, Trissino, Vicenza, Italy. 1 b Dipartimento di Chimica Industriale Toso Montanari, Viale Risorgimento 4, Bologna, Italy. The insertion of perfluorinated moieties within the structure of more traditional organic compounds confers unique properties that have been largely exploited in several application fields. The readily available allyl perfluoroalkyl ethers can be either converted to vinyl perfluoroalkyl ethers derivatives via a versatile and convenient double bond isomerization reaction or, in a completely different manner, used to build-up multi-block molecules, in which perfluorinated chains are alternated to hydro-ether segments. 2 In this work we present the ruthenium-catalyzed isomerization of the allyl ethers shown in. The isomerization has been carried out under variety of experimental conditions using conventional ([RuClH(C)(PPh 3) 3]) and less conventional (CatMETium_RF3 ) ruthenium(ii) complexes. The activity of the two different pre-catalysts together with the corresponding kinetic studies will be discussed. a Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier / CRS UMR 5069; 118 Route de arbonne, Toulouse, France; b Institut de Chimie de Toulouse, 118 Route de arbonne, Toulouse, France; c Institut des Sciences Analytiques et de Physico- Chimie pour l Environnement et les Matériaux, Université de Pau et des Pays de l Adour / CRS UMR 5254, Hélioparc, 2 Avenue du Président Angot, Pau, France; During the last 15 years gold chemistry experienced an impressive development regarding catalytic applications and thus gold complexes are no longer considered as chemically inert species. 1 Moreover, recent fundamental studies highlighted that the organometallic chemistry of gold complexes extends beyond the coordination/activation of π-bonds and that gold may offer a more versatile reactivity. 2 However, our knowledge of gold chemistry is still limited as compared to the other transition metals, which is especially true for elementary steps often involved in transition metal-mediated transformations such as oxidative addition, migratory insertion, etc. We recently started a research program aiming at investigating the fundamental reactivity of gold complexes. 3,4 In this context, we discuss an elementary step which is ubiquitous in transition metal chemistry but unprecedented with gold, namely syn insertion. 5 Alkynes and allenes are shown to insert into Au-Si bonds of (phosphine)silylgold complexes to yield vinylgold complexes with high stereo- and regioselectivity (Fig. 1). 6 Based on a combined experimental and theoretical study a mechanistic proposal is presented. The vinyl perfluoroalkyl ethers derivatives thus obtained can be used as attractive monomers in cationic UV-radiation curing technology. [2] [1] Miteni S.p.A.( is part of I.C.I.G. (International Chemical Investors Group ( an industrial group composed by 16 chemical companies, operating worldwide in base chemicals, fine chemicals, and polymers. [2] (a) Kirsch, P.; Modern fluoroorganic chemistry: synthesis, reactivity, applications, 2004, Wiley-VCH. (b) Siegemund, G.; Schwertfeger, W.; Feiring, A.; Smart, B.; Behr, F.; Vogel, H.; McKusick, B; Fluorine Compounds, rganic in Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim. (c) Dolbier, W. R. J. Fluorine Chem. 2005, 126, 157. (d) Berger, R.; Resnati, G.; Metrangolo, P.; Weber E.; Hulliger, J. Chem. Soc. Rev., 2011, 40, (e) Vincent, J.M. Chem. Commun. 2012, 48, [2] Crivello J.V.; Liu S.S. J. Polym. Sci. Part A Polym. Chem. 1997, 36, : Direct syn insertion into the Au-Si bond [1] Hashmi, A. S. K.; Toste, D. F.;. Modern Gold Catalyzed Synthesis; John Wiley & Sons, [2] Liu, L.-P.; Hammond, G. B. Chemical Soc. Rev. 2012, 41, [3] Gualco, P.; Ladeira, S.; Miqueu, K.; Amgoune, A.; Bourissou, D. Angew. Chem. Int. Ed. 2011, 50, [4] Gualco, P.; Ladeira, S.; Miqueu, K.; Amgoune, A.; Bourissou, D. rganometallics 2012, 31, [5] Hartwig, J. F. rganotransition Metal Chemistry: From Bonding to Catalysis; Palgrave Macmillan, [6] Joost, M.; Gualco, P.; Mallet-Ladeira, S.; Amgoune, A.; Bourissou, D. Angew. Chem. Int. Ed. 2013, in press. PSTERS
22 PSTERS Poster 13 Device Compatible Water xidation Catalysts for Solar to Chemical Energy Conversion J. M. Koelewijn,* D. G. H. Hetterscheid, G. Ciancaleoni, J.H.Reek Van t Hoff Institute for Molecular Sciences, Faculty of Science, University of Amsterdam, Science park 904, 1098 XH Amsterdam, The etherlands In 2001, the global energy consumption rate was 13.5 TW. In 2050 based on the increasing population and economic growth, this is estimated to reach 27 TW. 1 To meet these future demands, not relying on fossil fuels only, we need sustainable, carbon neutral ways of winning energy. The sun is the most abundant energy source on the planet (regarding current technology) as on average the energy of the sun reaching the earth s surface is estimated to be TW. Part of this can be directly used by converting it to electricity using solar cell technology, but it is essential to at least partly convert to storable energy, by fixing it in chemical bonds. This can be achieved by using solar energy to convert water into hydrogen and oxygen. Plants, algae and cyanobacteria already use photosynthesis to convert energy from the sun into chemical energy within Photosystem II at the water oxidation reaction center of the Manganese-Calcium cluster. With ature serving as a model we try to develop new, rapid and efficient water oxidation catalysts based on Iridium. 2 Application of suitable ligands offer ease of synthetic modification such that these catalysts can be modified to have the ability to integrate them into devices, which are capable to split water into hydrogen and oxygen. This so called Artificial Leaf, if turnover numbers and turnover frequencies are sufficiently high, could provide us with a significant solution towards the upcoming energy problem. In this work we will discuss our endeavors in catalyst modification. [1] Lewis,. S.; ocera, D. PAS 2006, 103, [2] Hetterscheid, D. G. H.; Reek, J. Chem. Commun. 2011, 47, Poster 14 Study of the Surface Chemistry of Ruthenium anoparticles in the Fisher-Tropsch Synthesis Luis Miguel Martinez-Prieto, a,b * Fernando ovio, a,b Karine Philippot, a,b Bruno Chaudret c a CRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de arbonne, BP44099, F Toulouse Cedex 4, France; b Université de Toulouse, UPS, IPT, F Toulouse Cedex 4, France; c Laboratoire de Physique et Chimie de ano-bjects, Institut ational des Sciences Appliquées 135 avenue de Rangueil, 31077, Toulouse, France; An ideal solution to the limit stock of natural sources of hydrocarbons and to control the C and C 2 emissions is the Fisher- Tropsch synthesis; C and C 2 are hydrogenated to produce hydrocarbons (olefins and paraffins) (Scheme 1). Although the activity and selectivity of this process have been improved over several decades, 1 fundamental issues about the mechanism and the structure of the catalyst remain unsolved. catalyst C/C 2 + H 2 C n H (2n+2) (alkanes), C n H 2n (olefins) Scheme 1 The development of more active and/or selective catalysts for industrial application of this process is still an ongoing field of research. Metal nanoparticles as catalysts are expected to provide more efficient and selective catalysis. In this context, our team has developed for over 20 years the synthesis of metal nanoparticles (Ps) following an organometallic approach (). 2 This method allows the tuning of Ps surface chemistry through addition of appropriate ligands as stabilizers. Moreover, the study of Ps surface properties is performed by using a combination of techniques such as IR-FT and MR spectroscopies. For example, RuPs prepared in this way can bring useful information on the coordination, dynamics and reactivity of surface ligands such as hydrides and C 3 which are present in many catalytic processes, like in the Fisher-Tropsch synthesis. [1] Schulz, H. Short History and Present Trends of Fisher-Tropsch Synthesis. Appl. Catal. A: Gen. 1999, 186, 3. [2] rganomatallic derived-i: Metals, Colloids and anoparticles, Philippot K. and Chaudret B., in Comprehensive rganometallic Chemistry III, Carbtree R. H. & Mingos M. P. (Eds.: In chief), Elsevier, Vol 12; Patricia, L.; Philippot, K.; Chaudret, B. ChemCatChem 2013, 5, 28 [3] ovio, F.; Philippot, K.; Chaudret, B. Catal. Lett. 2010, 140, 1.
23 Poster 15 Selective Synthesis of the [i 36 Co 8 C 8 (C) 48 ] 6 Carbonyl Cluster by Thermal Decomposition of the [H 2 i 22 Co 6 C 6 (C) 36 ] 4 Iacopo Ciabatti, a * Fabrizia Fabrizi de Biani, b Cristina Femoni, a Maria Carmela Iapalucci, a Giuliano Longoni a and Stefano Zacchini a Poster 16 Catalytic Hydrogenations Using a Water Soluble Pyridine-Triazole Ligand Md. Mahbubul Alam, a* Stefano Paganelli, a Valentina Beghetto, a Alberto Scrivanti, a Ugo Matteoli a a Department of Molecular Sciences and anosystems, Ca Foscari, University of Venice, Dorsoduro 2137, Venice, Italy, a Dipartimento di Chimica Industriale Toso Montanari, Viale Risorgimento Bologna (B), Italy; b Dipartimento di Chimica, Università di Siena, Via De Gasperi 2, Siena (SI), Italy; Several bimetallic i-co carbide and acetylide carbonyl clusters are known. They display a random alloy architecture with a very wide variability of the i/co composition. The i-co ratio ranges from 0.33 of [Co 6i 2C 2(C) 16] 2-1 to 9 of [i 9Co(C) 16] The possibility of preparing bimetallic i-co molecular clusters with very different i/co compositions makes these clusters quite attractive for the preparation of bimetallic magnetic i-co nanoparticles, allowing a gradual variation of their properties. 3 In addition, they are interesting also at the molecular level for the study of the relationship existing between composition and proprieties of bimetallic nanoclusters and nanoparticles. 4 Herein, our recent results in the chemistry of i-co carbonyl clusters are described. The thermal decomposition in thf of the hexa-carbide [H 2i 22Co 6C 6(C) 36] 4 [2] results in the new bimetallic i-co octacarbide [H 6 ni 36Co 8C 8(C) 48] n (n = 3-6), which possesses polyhydride nature and can be inter-converted by means of acid-base reactions. 5 The hydride nature of the [H 6 ni 22Co 6C 6(C) 36] n (n = 3-6) anions is suggested by the observed shifts of their υ(c) bands as a function of the basicity of the solvent and/or after addition of acids or bases, and fully confirmed by electrochemical studies. The hexa-anion [i 36Co 8C 8(C) 48] 6 has been isolated in a crystalline state and structurally characterized via X-ray crystallography. The high nuclearity [H 6 ni 36Co 8C 8(C) 48] n (n = 3-6) cluster approaches the nanosize regime since it displays a diameter of ca nm. Thus, it may be viewed as a molecular ultra-small metal nanoparticle. 6 [1] Ceriotti, A.; Della Pergola, R.; Longoni, G. J. rganomet. Chem. 1987, 330, [2] Ciabatti, I.; Femoni C.; Iapalucci, M. C.; Longoni, G.; Zacchini, S. rganometallics, 2012, 31, [3] Adams, R. D.; Trufan, E. Philos. Trans. R. Soc. A 2010, 368, [4] Zacchini, S. Eur. J. Inorg. Chem. 2011, [5] Ciabatti, I.; Fabrizi de Biani, F.; Femoni C.; Iapalucci, M. C.; Longoni, G.; Zacchini S. Dalton Trans. 2013, 42, [6] Quian, H. F.; Zhu, M. Z.; Wu, Z. K.; Jin, R. C. Acc. Chem. Res., 2012, 45, [5] hguchi, K.;Tanakab, T.; Kidoc, T.; Babac, K.; Iinumad, M.; Matsumotoa, K.; Akaoa, Y.; ozawa, Y. Biophys. Res. Commun. 2003, 307, 861. The liquid-liquid two-phase catalysis is at present of great interest because the catalyst is confined in one of the twophases and the product in the other phase allowing for a prompt recovery of the product and an easy recycle of the catalyst. In particular, the use of water soluble catalysts for aqueous/organic biphasic reactions is increasingly attractive 1. ur research group has long been interested in the synthesis of triazole ligands for Suzuki-Miyaura (S-M) cross-coupling reaction of aryl halides with arylboronic acids, and recently we have developed a water soluble pyridyl-triazole ligand for S-M reaction in water 2,3,4. In this work, we wish to report our studies on in situ biphasic (water/toluene) catalytic hydrogenation of unsaturated substrates in the presence of triazole ligand (L1) and [Ir(CD)Cl] 2. (a) (b) S 3 a + 3 H 2 M/L1 H 2 M/L1 Cu(I) M: [Ir(CD)Cl] 2 + Solvents: Water /Toluene + H + L1 H S 3 a Scheme 1. (a) Synthesis of ligand (L1), (b) Aqueous biphasic hydrogenation of 2-cyclohexen-1-one and 1,3-diisopropenylbenzene. [1] (a) Cornils, B.; Herrmann, W. A.; Horvath, I. T.; Leitner, W.; Mecking, S.; livier-bourbigou, H.; Vogt (Eds.) D. Multiphase Homogeneous Catalysis, Wiley-VCH, Weinheim, (b) Joo, F. Aqueous rganometallic Catalysis, Kluwer Acad. Publ. Dordrecht, [2] Amadio, E.; Scrivanti, A.; Chessa, G.; Matteoli, U.; Beghetto, V.; Bertoldini, M.; Rancan, M.; Venzo, A.; Bertani, R. J. rg. Chem. 2012, 716, 193. [3] Amadio, E.; Bertoldini, M.; Scrivanti, A.; Chessa, G.; Beghetto, V.; Matteoli, U.; Bertani, R.; Dolmella, A. Inorg. Chim. Acta 2011, 370, 388. [4] Amadio, E.; Bertoldini, M.; Beghetto, V.; Scrivanti, A.; Chessa, G.; Matteoli, U. WISPC 2012, Bressanone, 29 January to 3 February, PSTERS
24 PSTERS Poster 17 ovel dicarbene iridium(iii) catalysts for water oxidation reaction Poster 18 A new palladium-catalyzed carbonylative approach to isobenzofuran derivatives Andrea Volpe, a* Cristina Tubaro, a Andrea Sartorel, a,b Laura Meneghini, a Marilena Di Valentin, a Claudia Graiff, c Marcella Bonchio a,b a Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo 1, 35131, Padova; b Istituto per la Tecnologia delle Membrane del CR, US di Padova, via Marzolo 1, Padova; c Dipartimento di Chimica, Università di Parma, viale delle Scienze 17/A, Parma; Light driven catalytic water splitting could contribute to the obtainment of sustainable energy sources alternative to fossil fuels. 1a This process leads to the green production of H 2 and 2 molecules, but it has still a bottleneck represented by the development of an efficient catalytic system for the oxidative half reaction, which is endoergonic and mechanistically rather complex. 1 Several transition metals have been employed so far, both in heterogeneous or in homogeneous conditions. 2 ne of the most active species is Ir 2 nanoparticles, 3 but molecular complexes are more attractive because their steric and electronic properties can be finely modulated by playing on the metal coordination sphere. 2 In this contribution we report novel dicarbene iridium(iii) complexes with different nuclearity depending on the nature of the coordinated -eterocyclic dicarbene ligands. Some of the synthesized complexes have been employed as catalyst for water oxidation reaction both in dark conditions (Ce(IV) or ai 4 as sacrificial oxidant) or in a photoactivated cycle ([Ru(bpy) 3] 2+ as photosensitizer and a 2S 2 8 as sacrificial electron acceptor). Finally the catalyst fate under turnover conditions has been investigated by combined spectroscopic (MR, EPR, UV-Vis), kinetic and GC-MS experiments. 4 Raffaella Mancuso, Ida Ziccarelli,* Donatella Armentano, Bartolo Gabriele Department of Chemistry and Chemical Technology, Università della Calabria, Via P. Bucci 12/C, Arcavacata di Rende (CS), Italy, The 3H-isobenzofuran unit constitutes the core structure of several biological active compounds having antiinflammatory, antiviral, and antimicrobial. 1 In this communication, we report a novel approach to the synthesis of functionalized 3H-isobenzofuran-1-ylideneamine derivatives 2, based on PdI 2-catalyzed oxidative heterocyclizationalkoxycarbonylation 2 of readily available 2-alkynylbenzamides 1, according to Scheme 1. R 2 PdI 2 /KI C, 2, R'H HR 1 R (R 1, R 2 = H, alkyl, aryl PdI 2 R' = Me, Et) C, R'H [Pd(0)+HI] PdI 2 R 2 IPd R 2 HR 1 HI R' 2 C R 1 R 2 Pd(0) + 2 HI + (1/2) 2 Scheme 1 PdI 2 + H 2 Reactions are carried out in alcoholic solvents (R'H, R' = alkyl) at C and under 40 atm of a 4:1 mixture of Cair, in the presence of catalytic amounts of PdI 2 (1 mol %) in conjunction with KI (10 mol %), to give carbonylated 3H- Isobenzofurans 2 in fair to good isolated yields (50-80%). The structure of the products has been confirmed by X-ray diffraction analysis. [1] (a). S. Lewis, D. G. ocera, Proc. atl. Acad. Sci. U.S.A., 2006, 103, 15729; (b) X. Sala, L. Romero, M. Rodriguez, L. Escriche, A. Llobet, Angew. Chem. Int. Ed., 2009, 48, 2842; (c) K. J. Young, L. A. Martini, R. L. Milot, R. C. Snoeberger III, V. S. Batista, C. A. Schmuttenmaer, R. H. Crabtree, G. W. Brudvig, Coord. Chem. Rev., 2012, 256, [2] B. Limburg, E. Bouwman, S. Bonnet, Coord. Chem. Rev. 2012, 256, [3] J. Kiwi, M. Grätzel, J. Am. Chem. Soc., 1979, 101, [4] A. Volpe, A. Sartorel, C. Tubaro, L. Meneghini, M. Di Valentin, C. Graiff, M. Bonchio, submitted. [1] For biological activity of 3H-isobenzofuran derivatives see: (a) Hess, M.; Elfringhoff, A.S.; Lehr, M. Journal of enzyme inhibition and medicinal chemistry, 2008, 23,6, (b) Maresh, J.; Zhang, J.; Tzeng, Y.L.; Goodman,. A.; Lynn, D. G. Bioorganic and Medicinal Chemistry Letters. 2007, 17, 12, (c) Lin, X; Huang, YJ; Fang, MJ; Wang, JF; Zheng, ZH; Su, WJ. Fems Microbiology Letters. 2005, 251, (d) Carta, A.; Sanna, P.; Bacchi, A. Heterocycles, 2002, 57, [2] For reviews, see: (a) Gabriele, B.; Mancuso, R., Salerno, G. Eur. J. rg. Chem, 2012, 35, ; (b) Gabriele, B.; Salerno, G.; Costa, M. Top. rganomet. Chem. 2006, 18, (c) Gabriele, B.; Salerno, G. PdI2. In e-ers (Electronic Encyclopedia of Reagents for rganic Synthesis); Chrich, D., Ed.; Wiley-Interscience: ew York, (d) Gabriele, B.; Salerno, Costa, Synlett 2004, (e) Gabriele, B.; Salerno, G.; Costa, M.; Chiusoli, G. P. Curr. rg. Chem. 2004, 8, (f) Gabriele, B.; Salerno, G.; Costa, M.; Chiusoli, G. P. J. rganomet. Chem. 2003, 687, (g) Gabriele, B.; Salerno, G. Cyclocarbonylation. In Handbook of rganopalladium Chemistry for rganic Synthesis; egishi, E., Ed.; Wiley-Interscience: ew York,2002.
25 Poster 19 Intramolecular d 10 -d 10 Interactions in Bimetallic Co-Au Carbide Carbonyl Cluster Mohammad Hayatifar,* Cristina Femoni, Maria C. Iapalucci, Giuliano Longoni, Stefano Zacchini Dipartimento di Chimica Industriale 'Toso Montanari', Viale Risorgimento 4, 40136, Bologna Italy; Weak d 10 -d 10 metal-metal interactions are now widely documented in the chemistry of Au(I) complexes and clusters, and the term aurophilicity is commonly used to refer to such interactions. 1 Although positively charged Au(I) ions could be expected to repel each other on the basis of electrostatics, the attractive interactions between these closed valence shell ions result in interatomic distances typically in the range between 2.7 and 3.3 Å, often shorter than the sum of the van der Waals radii. 2 The M 6C octahedral framework present in several mono-carbide carbonyl clusters seems to be an interesting platform in order to test aurophilicity. In these clusters, the [AuPPh 3] + fragment might be coordinated to an edge or a face of the octahedron. Moreover, when a second fragment is added, several options arise since it can coordinate to a site close or far from the first one. Aurophilicity favors the proximity of the two Au(I) centers and the formation of intramolecular d 10 -d 10 interactions, as exemplified in Rh 6C(C) 13(AuPPh 3) 2 and Co 6C(C) 13(AuPPh 3) 2. 3,4 Poster 20 A Cooperative Iridium-bisMETAMRPhos Complex for the Dehydro-genation of Formic Acid S. ldenhof, a* B. de Bruin, a J.I. van der Vlugt, a J.H. Reek a van t Hoff Institute for Molecular Sciences, University of Amsterdam, The etherlands. Hydrogen holds the potential to be one of the major energy carriers for the future. However, a hydrogen-based economy requires technology that allows efficient and safe storage and release of H 2. In this light, the reversible storage of hydrogen in the form of formic acid provides an interesting H 2 storage-release system. Substantial developments in the production of formic acid since the early nineties have stimulated interest in the reverse reaction for hydrogen release on demand. 1 Ideally, catalytic dehydrogenation takes place in the absence of base and additives, thereby maximizing the overall hydrogen storage capacity and preventing hydrogen contamination with traces of volatile amines that may poison the fuel cell. We envisioned ligand cooperativity could provide an interesting approach in this area as metal complexes with an internal base as part of the ligand could be developed. In this contribution we present a novel iridium-bismetamrphos complex that is active in formic acid dehydrogenation in the absence of external base, and demonstrate that the ligand plays an active role in the mechanism by pre-assembling formic acid, stabilizing the transition state (see figure 1) and the deprotonation of formic acid (see figure 2). 2 It was, thus, of interest to investigate analogous octahedral M 6C carbonyl clusters containing more than two [AuPPh 3] + fragments, in order to see if more extended Au Au interactions were formed and to evaluate the importance of such interactions in larger clusters. Herein, we report the study of the reaction of [Co 6C(C) 15] 2 with Au(PPh 3)Cl which results in the formation of some new Co-Au carbide carbonyl clusters. Among these, the neutral Co 6C(C) 12(AuPPh 3) 4 cluster has been structurally characterized, showing the existence of at least three different isomers possessing the same octahedral Co 6C core and differing for the coordination modes of the AuPPh 3 fragments. [1] Schmidbaur, H.; Schier, A. Chem. Soc. Rev. 2012, 41, 370. [2] Voβ, C.; Pattacini, R.; Braunstein, P. C. R. Chim. 2012, 15, 229. [3] Fumagalli, A.; Martinengo, S.; Albano, V. G.; Braga, D.; Grepioni, F. J. Chem. Soc. Dalton Trans. 1989, [4] Reina, R.; Riba,.; Rossell,.; Seco, M.; de Montauzon, D.; Pellinghelli, M. A.; Tiripicchio, A.; Font-Bardía, M.; Solans, X. J. Chem. Soc. Dalton Trans. 2000, Figure 2 [1] (a) Fellay, C.; Dyson, P. J.; Laurenczy, G. Angew. Chem. Int. Ed. 2008, 47, (b) Loges, B.; Boddien, A.; Junge, H.; Beller, M. Angew. Chem. Int. Ed. 2008, 47, (c) Boddien, A.; Mellmann, D.; Gärtner, F.; Jackstell, R.; Junge, H.; Dyson, P. J.; Laurenczy, G.; Ludwig, R.; Beller, M. Science 2011, 333, [2] ldenhof, S.; de Bruin, B.; Lutz, M.; Siegler, M. A.; Patureau, F. W.; van der Vlugt J. I.; Reek,. H. J. Chem. Eur. J. 2013, doi: /chem PSTERS
26 PSTERS Poster 21 Synthesis of Electron-Rich Uranium(IV) Complexes Supported by Tridentate Schiff Base Ligands and Their Multi-Electron Redox Chemistry Poster 22 Borrowing Electrons to Induce oble Metal Reactivity on First Row Transition Metal Complexes Clément Camp a, Julie Andrez a, Jacques Pécaut, a Marinella Mazzanti* a D. L. J. Broere,* J. I. van der Vlugt alaboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E CEA / UJF-Grenoble 1, IAC, CEA-Grenoble, 17 rue des Martyrs, Grenoble, F-38054, France Homogeneous & Supramolecular Catalysis, Van t Hoff Institute for Molecular Sciences, University of Amsterdam, The etherlands; * Metal based multi-electron processes remain uncommon in uranium chemistry 1 especially in comparison with the d-block metals, the chemistry of low-valent uranium being dominated by single-electron transfers. In this context, the association of uranium to a non-innocent ligand acting as an independent electron reservoir at a same molecule represents an attractive alternative that should render multi-electron reactivity possible while stabilizing highly reactive formally lowvalent oxidation states. 2 We recently reported the synthesis, structure and reactivity of a new complex of U(IV) with the tridentate Schiff base ligand Me naphtquinolen. 3 The [U(μ-bis- Me naphtquinolen)] 2 dimer 2 was isolated from toluene confirms the presence of a U(IV) complex of the reduced ligand. Reactivity studies with molecular oxygen and 9,10- phenanthrenequinone show that complex 2 can act as a multi-electron reducing agent releasing two electrons trough the cleavage of the C-C bond to restore the original imino function of the ligand (). A major challenge in replacing noble metals by earth abundant metals in homogeneously catalyzed processes is the difference in electronic structure and behavior of these subsets of transition metals. First-row transition metals are more prone to undergo one-electron oxidation and reduction reactions, whereas a metal such as platinum often favors twoelectron redox changes for bond cleavage or formation reactions. 1 The use of redox-active ligands as electron reservoirs for first-row transition metal complexes can give them noble metal reactivity. In this scenario, the redox-changes required for elementary reactions, such as oxidative addition and reductive elimination, can be partly or fully ligand centered. 2-4 [1] Evans, W. J.; Kozimor, S. A. Coord. Chem. Rev. 2006, 250, [2] Schelter, E. J.; Wu, R. L.; Veauthier, J. M.; Bauer, E. D.; Booth, C. H.; Thomson, R. K.; Graves, C. R.; John, K. D.; Scott, B. L.; Thompson, J. D.; Morris, D. E.; Kiplinger, J. L. Inorg. Chem. 2010, 49, [3] Camp, C.; Andrez J.; Pécaut J.; Mazzanti M. Inorg. Chem., 2013, 52, Scheme 1 The latest findings on the design, characterization and initial reactivity of new redox-active ligands and their corresponding transition metal complexes will be presented. We will focus on the implementation of an,-coordinated o- aminophenolato moiety into a tridentate ligand framework and its chemistry with group 10 transition metals. [1] Wieghardt, K; Chirik, P. Science 2010, 327, [2] Ward, T.R. et al., Angew. Chem. Int. Ed. 2012, 51, [3] de Bruin, B. et al., Angew. Chem. Int. Ed. 2011, 50, [4] van der Vlugt, J.I. Eur. J. Inorg. Chem. 2012,
27 Poster 23 Chelating Heteroditopic Bis-HCs Complexes: Synthesis and Application in Catalytic Hydrogenation Poster 24 ew Catalytic Systems for the Simultaneous Lipids and Free Acids Trans- Esterification/Esterification in non Aqueous Systems S. Sluijter, a * C. J. Elsevier a V. Benessere,*,a,b M. E. Cucciolito, a,b G. Dal Poggetto, a M. Di Serio, a,b F. Ruffo, a,b R. Vitiello a,b a Van t Hoff Institute of Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam, 1098 XH, The etherlands Following the success of monodentate -Heterocyclic Carbenes (HCs), chelating bis-hcs have become popular ligands in transition metal catalysis. 1 Two strongly bound HCs lead to enhanced stability of the complex due to the chelate effect as well as an electron-rich metal center. After reporting zero- and divalent palladium complexes bearing classic bis-carbene ligands (a), 2 we are now interested in mixed HC-1,2,3-triazolylidene complexes (Figure 1b). In this system, a well-known and accessible class of mesoionic carbenes (MICs) is combined with a normal HC, leading to heteroditopic bis-hc complexes. MICs, called that way because a resonance structure with all-neutral formal charges cannot be drawn for the free ligand (c), are generally even stronger electron donors than regular HCs. 3,4 The different HCs may in synergy induce novel reactivity patterns. a Dipartimento di Scienze Chiniche, Università di apoli Federico II, Italy; b CIRCC, Università di Bari, via Celso Ulpiani 27, Bari, Italy Biodiesel (a mixture of Fatty Acid Methyl Esters, FAME) is the second biofuel produced in the world and the first in Europe. Biodiesel is produced today by trans-esterification of triglycerides of refined/edible type oils using methanol and an alkaline homogeneous catalyst (ah, ame) (scheme 1): RC 2 2 CR 2 CR + 3 MeH Scheme 1 H 3 RC 2 Me + H H The reaction is normally performed at C, and glycerol and FAME s are separated by settling after catalyst neutralization. The crude glycerol and biodiesel are then purified. However, homogeneous alkaline catalysts cannot directly be used with waste oils due to the presence of large amounts of free fatty acids (FFA). 1 Use of Lewis acid catalysts, able to promote the simultaneous esterification of FFA and trans-esterification of glycerides, 1-3 is an elegant way solve this problem. 3 Within this frame, we have developed an active supported homogeneous Zn acid catalyst (in figure 1), linked to a solid silica support by an urethane bond. This choice combines the advantage of homogeneous acid catalysis with the possibility to recover and re-use the catalyst by simple filtration. Synthetic and catalytic details will be given in the poster. : General structure of classic bis-hc (a), mixed HC-MIC (b) complex and the free carbene of a 1,2,3-triazolylidene compared to a normal HC (c), showing its mesoionic character. The HC-MIC ligands can be obtained by alkylation of the -3 position of the imidazolium-triazole salts, that are easily accessible via click chemistry. 5 The coordination of the ligands to late transition metals and the catalytic reduction activity of unsaturated bonds of the resulting complexes have been studied and will be discussed. Preliminary studies show good activity of the HC-MIC complexes in the (transfer) hydrogenation of ketones and several esters. Zn Cl Cl C()H(CH 2 ) 3 Si [1] Mata, J. A.; Poyatos, M.; Peris, E. Coord. Chem. Rev. 2007, 251, 841. [2] Sluijter, S.; Warsink, S.; Lutz, M.; Elsevier, C. J. Dalton trans. 2013, 42, [3] Crabtree, R. H. Coord. Chem. Rev. 2013, 257, 755. [4] Mathew, P.; eels, A.; Albrecht, M. J. Photoimpact 6 italiano google docs. Am. Chem. Soc. 2008, 130, [5] Warsink, S.; Drost, R. M.; Lutz, M.; Spek, A. L.; Elsevier, C. J. rganometallics 2010, 29, Acknowledgements: Financial support: P Project cod. P 01_01966 (EERBICHEM). [2] Lotero, E.; Liu, Y.; Lopez, D. E.; Suwannakaran, K.; Bruce, D. A.; Goodwin, J. G., Jr. Ind. Eng. Chem. Res. 2005, 44, [3] Di Serio, M.; Tesser, R.; Pengmei,L.; Santacesaria, E. Energy & Fuels 2008, 22, [4] Sharma, Y.C.; Bhaskar Singh, B.; Korstad, J. Biofuels, Bioprod. Bioref. 2011, 5, Piccinelli, F. Inorg. Chem., 2008, 47, PSTERS
28 PSTERS Poster 25 Synthesis of Biological Aza-Compounds Catalysed by Ruthenium Porphyrins Paolo Zardi, a * Alessandro Caselli, a Piero Macchi, b Giorgio Tseberlidis, a Emma Gallo a a Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi 19, Milano (MI), Italy; b University of Berne, Department of Chemistry & Biochemistry, Freiestrasse 3, CH-3012 Berne, Switzerland; Poster 26 Copper-Mediated Intramolecular Alkoxychlorination f Alkynes as a Route to Chloroalkyliden-Substituted Heterocycles Silvia Gazzola,* Gianluigi Broggini, Filippo Brusa, Elena Pangher Dipartimento di Scienza e Alta Tecnologia, Via Valleggio 11, Como, Italy, The development of clean and efficient methods to synthesise nitrogen-containing molecules is a topic of high interest in order to obtain valuable fine chemicals in a cheap and environmentally-friendly way. The benzylic amination of hydrocarbons using rutheniumporphyrin complexes as catalysts and aryl azides as nitrene sources is an effective strategy to achieve this aim. 1 The so-obtained good results prompted us to extend the reaction scope to the synthesis of products of pharmaceutical and biological interest. The Ru(TPP)C-catalysed benzylic amination of methyl phenylacetate and methyl dihydrocinnamate is an efficient synthetic methodology to achieve a and b aminoesters respectively (1,2) (Scheme 1) (TPP = dianion of tetraphenylporphyrin). Furthermore, using methyl 3-phenyllactate derivatives as substrate, -oxy - aminoacids (3,4), useful -lactames precursors, were obtained in good yields (Scheme 1). All the reactions were carried out in refluxing benzene under nitrogen atmosphere; a high excess of substrate is required, but it can be easily recovered by vacuum distillation. Scheme 1 During the catalytic amination, a bis-amido ruthenium complex is always formed as a resting state. This complex was isolated and fully characterized in the case of the amination of methyl phenylacetate (). The formation of oxygen-carbon bonds has a crucial role in organic chemistry. 1 Intramolecular alkoxylation of carboncarbon multiple bonds represents one of the most effective approaches to prepare oxygenated heterocycles, which are important motifs in many biologically active compounds. This reaction increases its interest when involved in domino processes. In this context, beside the classical use of the hydroxy group, transition metal-catalyzed alkoxylations involving secondary amides 2 or ureas 3 have already been used as a tool to perform oxygenated heterocycles. Following this concept, we tried to perform domino processes involving a cyclization followed by the formation of a carbon-halogen bond. Thus, here we describe a new method to prepare heterocylic derivatives bearing a chloroalkyliden group by intramolecular alkoxychlorination of alkynes tethered to secondary amides or ureas (). The reactions were carried out in acetonitrile at reflux by using copper chloride in stoichiometric amount as both promoter and chlorine source as well as copper chloride in catalytic amount as promoter and CS as chlorine source. [1] (a) Intrieri, D.; Mariani, M.; Caselli, A.; Ragaini, F.; Gallo, E.; Chemistry 2012, 18, (b) Fantauzzi, S.; Caselli A.; Gallo, E.; Dalton Trans 2009, 28, [1] Enthaler, S.; Company, A. Chem. Soc. Rev. 2011, 40, [2] Beccalli, E. M.; Borsini, E.; Broggini, G.; Palmisano, G.; Sottocornola, S. J. rg. Chem. 2008, 73, [3] Fujino, D.; Hayashi, S.; Yorimitsu, H.; shima, K. Chem. Commun. 2009, 5754.
29 Poster 27 onsymmetric -Diimines in Pd-Catalyzed Ethylene/Polar Monomer Copolymerization V. Rosar, a * A. Meduri, a,b T. Montini, a P. Fornasiero, a E. Zangrando, a B. Milani a Poster 28 Mild Regioselective Palladium-Catalyzed Direct C-H Arylation of Azoles Chiara Manzini, * Fabio Bellina, icola Guazzelli, Marco Lessi, Luca Perego a Department of Chemical and Pharmaceutical Sciences, University of Trieste, Italy, b Department of Sciences and Technologies, University of Sannio, Benevento, Italy ne of the major unsolved problems in polymer chemistry is represented by the efficient copolymerization of terminal alkenes with polar vinyl monomers to yield functionalized polyolefins. 1 The main catalytic systems reported in literature are based on palladium(ii) complexes with either -diimines or phosphino-sulphonate ligands, 2 but their productivity is far too low for any industrial application, thus better performing catalyst are strongly needed. Recently, we have reported a new nonsymmetric -diimine ligand featured by an acenaphthenequinone (Ar,Ar -BIA) skeleton with one aryl ring substituted on meta positions with electron-withdrawing groups and the other aryl ring bearing electron-donating substituents on the ortho positions. 3 The related Pd(II) monocationic complexes were found to be more productive than the complexes with the corresponding symmetrically substituted Ar-BIAs. 3 ow the library of the nonsymmetric Ar,Ar -BIAs has been extended to two new ligands, both characterized by an aryl ring bearing a methoxy and a methyl group on the ortho positions and differing in the positions of the electron-withdrawing groups (CF 3) on the other aryl ring (). The related neutral, [Pd(CH 3)Cl(Ar,Ar -BIA)], and monocationic, [Pd(CH 3)(L)(Ar,Ar -BIA)][PF 6] (L = CH 3C or dmso), palladium(ii) complexes have been synthesized and fully characterized in solution and, when suitable crystals were obtained, in solid state (Figure 2). The preferentially formed isomer is featured by the Pd-CH 3 bond trans to the Pd- bond of the CF 3-substituted aryl ring. Detailed investigations on the catalytic behaviour of the monocationic derivatives in the ethylene/methyl acrylate copolymerization, carried out at mild conditions of temperature and pressure, will be presented. Dipartimento di Chimica e Chimica Industriale, Via Risorgimento 35, Pisa, Italy, Arylazoles are important structural units frequently found in natural products, 1a pharmaceutics, 1b agrochemicals, 1c and organic functional materials. 1d Recently, the transition metal-catalyzed direct arylation reactions of azoles with aryl halides have emerged as an attractive strategy for the effective construction of Csp 2 -Csp 2 aryl-heteroaryl bonds. 2 These reactions, unlike the traditional metal-catalyzed cross-coupling protocols involving the use of preformed organometallics, enable the direct elaboration of heteroaromatic cores without the pre-activation of both the coupling partners. ver the last years we have been interested in studies aimed to broaden the substrate scope of the direct arylation of π- electron-rich heteroarenes and, in particular, to develop efficient protocols for the synthesis of aryl azoles involving palladium-catalyzed regioselective direct C-H arylations of azoles with aryl halides. We have recently found that tetrabutylammonium acetate, an organic base rarely used in direct arylation protocols, is able to promote an effective regioselective direct C-5 arylation of 1-methyl-1H-pyrazole, oxazole and thiazole with aryl bromides in the presence of Pd(Ac) 2 as the catalyst precursor at a reaction temperature of only 70 C (). 3 H C B A + Ar Br Pd(Ac) 2 (cat) Bu 4 Ac, DMA, 70 C Ar C B A A variety of 5-aryl-1-methylimidazoles was also very efficiently obtained simply rising the reaction temperature to 110 F 3 C F 3 C CF 3 Figure 2 C. 3 Moreover, we successfully achieved the one-pot sequential C-5 and C-2 direct arylations of oxazole and 1- methylimidazole by pairing this new protocol with our previously reported procedure for the regioselective ligandless direct C-2 arylation reaction. The application of this simple and effective protocol to the preparation of bioactive compounds and of new organic chromophores will be also showed and discussed. Figure 2 [1] akamura, A.; Ito, S.; ozaki, K. Chem. Rev. 2009, 109, [2] a) Johnson, L. K.; Mecking, S.; Brookhart, M. J. Am. Chem. Soc. 1996, 118, 267; b) Drent, E.; van Dijk, R.; van Ginkel, R.; van ort, B.; Pugh, R. I. Chem. Commun. 2002, 744. [3] Meduri, A.; Montini, T.; Ragaini, F.; Fornasiero, P.; Zangrando, E.; Milani, B. ChemCatChem 2013, 5, [1] a) Morinaka, B. J.; Pawlik, J. R.; Molinski, T. F. J. rg. Chem., 2010, 75, ; b) Selig, R.; Goettert, M.; Schattel, V.; Schollmeyer, D.; Albrecht, W.; Laufer, S. J. Med. Chem., 2012, 55, ; c) Leroux, P.; Lanen, C.; Fritz, R. Pestic. Sci., 2006, 36, , d) Liu, H.-H.; Chen, Y. Tetrahedron, 2013, 69, [2] Bellina, F.; Rossi, R. Tetrahedron, 65, 2009, and references cited therein. [3] Bellina, F.; Lessi, M.; Manzini, C. Eur. J. rg. Chem. 2013, accepted. DI: /ejoc PSTERS
30 PSTERS Poster 29 rganic Chromophores Based on a Fused Bis-Thiazole Core and their Application in Dye- Sensitized Solar Cells Alessio Dessì, a * Massimo Calamante, a Alessandro Mordini, a Maurizio Peruzzini, a Lorenzo Zani, b Gianna Reginato a a CR Istituto di Chimica dei Composti rganometallici (CR-ICCM), Via Madonna del Piano 10, Sesto Fiorentino (FI), Italy; b CR Istituto per la Sintesi rganica e la Fotoreattività (CR-ISF), Via Piero Gobetti 101, Bologna, Italy; Dye-Sensitized Solar Cells (DSSC) are one of the most promising technologies to convert solar energy in electric current because of their low cost of production and their colorful and decorative features. 1 The most important component of a DSSC is the sensitizer, which can be a totally organic molecule able to absorb solar light and to convert the absorbed energy into electric current. The organic sensitizer must have an appropriate structure, with a donor (D) and an acceptor (A) group linked by an unsaturated unit (π). Four new D-π-A organic dyes incorporating either a thiazolo[5,4-d] thiazole bicyclic system (TTZ1 2) or a benzo[1,2-d:4,5-d]bisthiazole tricyclic unit (BBZ1 2) have been synthesized and fully characterized. 2 Poster 30 Water Soluble Calix[4]pyrrole-based Bis[2]catenane Frank A. Arroyave, Pablo Ballester* Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans Tarragona, Spain, Calix[4]pyrrole, among many other interesting calixarenes used in supramolecular chemistry, are currently employed and considered for an assorted number of applications (e. g. catalysis, sensors, separations, etc.). We have found that calix[4]pyrroles, such as the nanocapsule shown in, can form supramolecular assemblies, and as well recognition of ionic and neutral guest species, 1-3 therefore, applications such as selective binding agents or molecule-separation agents can be envisioned. Many studies, have shown that the intermolecular interactions that form the calix[4]pyrrole supramolecular systems, not only occur in solid state, but also in solution. 4,5 Here, we present our efforts to produce these calix[4]pyrrole supramolecular assemblies in polar solvents, and in order to achieve this, we have included various carboxylic groups in the chemical structures forming the supramolecular assembly. The key steps of the synthesis include an efficient MW-assisted preparation of the thiazole[5,4-d] thiazole core and selective functionalization of two different dihalothienyl derivatives through Suzuki couplings. All the compounds showed photo- and electrochemical properties compatible with their employment in dye-sensitized solar cells. Dye-sensitized solar cells fabricated with those dyes yielded power conversion efficiencies up to 3.53%. [1] Hagfeldt A., Boschloo G., Sun L., Kloo L., Petterson H. M. Chem. Rev. 2010, 110, [2] Dessì A., Barozzino Consiglio G., Calamante M., Reginato G., Mordini A., Peruzzini M., Taddei M., Sinicropi A., Parisi M. L., Fabrizi de Biani F., Basosi R., Mori R., Spatola M., Bruzzi M., Zani L. Eur. J. rg. Chem. 2013, [1] Jain, V. K.; Mandalia, H. C. Heterocycles 2007, 71, [2] Gale, P. A.; Anzenbacher Jr, P.; Sessler, J. L. Coord. Chem. Rev. 2001, 222, [3] Custelcean, R.; Delmau, L. H.; Moyer, B. A.; Sessler, J. L.; Cho, W.-S.; Gross, D.; Bates, G. W.; Brooks, S. J.; Light, M. E.; Gale, P. A. Angew. Chem., Int. Ed. 2005, 44, [4] Gil-Ramirez, G.; Escudero-Adan, E. C.; Benet-Buchholz, J.; Ballester, P. Angew. Chem., Int. Ed. 2008, 47, [5] Ciardi, M.; Tancini, F.; Gil-Ramirez, G.; Escudero, A. E. C.; Massera, C.; Dalcanale, E.; Ballester, P. J. Am. Chem. Soc. 2012, 134,
31 Poster 31 Design of Photoswitchable Pt(II) and Ru(II) Complexes as Potential Antitumoral Agents Andreu Presa,* a Patrick Gámez, a Ivana Borilovic, a livier Roubeau b a Departament de Química Inorgànica, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, Barcelona, Spain; b Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC and Universidad de Zaragoza, Plaza San Francisco s/n, Zaragoza, Spain; Dithienylethenes of the type illustrated in are well-known for their promising behaviour as molecular switches, as they undergo reversible ring-closure upon irradiation with UV or visible light. 1-3 However, their potential application in biological systems has not been extensively studied yet. Here we present our first approach to the design of new photoswitchable Pt(II) and organometallic Ru(II) coordination compounds with dithienylethene ligands. These newly obtained compounds exhibit interesting optical properties, and are intended to undergo further studies of biological interaction. UV Vis R 1 S S R 2 R S S 1 R 2 Colorless Colored Poster 32 Carbonylative Synthesis of 10,11-dihydrobenzo[b,f][1,4]oxazepine Derivatives by Tandem Alkoxycarbonylation-Heterocyclization Raffaella Mancuso, Dnyaneshwar Raut,* Bartolo Gabriele Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, Via P. Bucci 12/C, Arcavacata di Rende (Cosenza); PdI 2-catalyzed oxidative alkoxycarbonylation- heterocyclization of acetylenic substrates bearing a suitably placed nucleophilic group is a powerful methodology for the direct synthesis of carbonylated heterocycles. 1 The process starts with an exo or endo intramolecular attack by the nucleophilic group to the triple bond coordinated to palladium, followed by carbon monoxide insertion and nucleophilic displacement to give the final product and Pd(0). The latter species in then reoxidized by the action of an external oxidant, usually molecular oxygen (Scheme 1). 1 In this communication, we report a novel application of this kind of reactivity to the direct synthesis of carbonylated 10,11-dihydrobenzo[b,f][1,4]oxazepine derivatives 2, starting from readily available 2-(2- alkynylphenoxy)anilines 1, according to Scheme 1. Reactions are carried out in an alcoholic solvent under relatively mild conditions (100 C and 40 atm of a 4:1 mixture of C-air for 24 h, using 2 mol % of PdI 2 in conjunction with 20 mol % of KI), to afford the desired products 2 in satisfactory yields (50-74%). PdI 2 PdI R - HI PdI and/or R YH Y R Y C, uh [Pd(0)+HI] C, uh [Pd(0)+HI] u Y R Pd(0) + 2 HI+ (1/2) 2 PdI 2 + H 2 Scheme 1 u R Y [1] Feringa, B. L. (Ed.), Molecular Switches, Wiley-VCH, Weinheim, [2] Irie, M. Chem. Rev. 2000, 100, [3] Hanazawa, M.; Sumiya, R.; Horikawa, Y.; Irie, M. J. Chem Soc., Chem Commun. 1992, 206. R 1 H 2 1 R 2 R 1 + C + (1/2) 2 + RH PdI 2 Pd(0) + 2 HI + (1/2) 2 H 2 PdI 2 HI R 2 PdI 2 + H 2 R 1 PdI 2 cat H R 1 H 2 (50-74%) R 2 R 2 PdI C 2 R C, RH [Pd(0)+HI] Scheme 2 [1] Gabriele, B.; Mancuso, R.; Salerno, G. Eur. J. rg. Chem, 2012, PSTERS
32 PSTERS Poster 33 ovel Uranyl Salophen Complexes Bearing Anthracenyl Side Arms: Synthesis and Photochemical Behavior Poster 34 Bioactive Ru(II)-Arene Complexes with atural Polyphenolic Ligands as Anticancer Metallodrugs Silvia Bartocci, a* Francesco Yafteh Mihan, a Alberto Credi, b Serena Silvi, b Antonella Dalla Cort a a Dipartimento di Chimica e IMC-CR, Università La Sapienza, P.zzle A. Moro 5, Rome, Italy; b Photochemical anosciences Laboratory and Center for the Chemical Conversion of Solar Energy (Solar Chem), Dipartimento di Chimica «Giacomo Ciamician», Università di Bologna, Via Selmi 2, Bologna, Italy; Fluorescence spectroscopy is a simple and high sensitive technique very useful for the detection of traces of analytes. Actually, in the last years, the design and the development of fluorescent supramolecular materials for sensing has became a target of main importance. 1 Simple uranyl salophen complexes are able to recognize neutral molecules and anions and the recognition event, is easily detected by variations in the UV-Vis and MR spectra but not in fluorescent emission spectra despite the fact that salophen ligand and uranyl salt are fluorescent if considered independently. In order to obtain uranyl salophen complexes with such characteristic, we tried to introduce fluorescent moieties within the basic skeleton of the receptors as in complexes 1 and 2 () Francesca Condello, a * Riccardo Pettinari, b Fabio Marchetti, a Claudio Pettinari, b Jessica Palmucci, a Serena rbisaglia, a Massimiliano Cuccioloni, c Anna Maria Eleuteri, c Valentina Cecarini, c Laura Bonfili, c Matteo Mozzicafreddo c a School of Science and Technology, Via S. Agostino 1, Camerino (MC), Italy; b School of Pharmacy, Via S. Agostino 1, Camerino (MC), Italy; c School of Bioscience and Biotechnology, via Gentile III da Varano, Camerino (MC), Italy; Ruthenium-arene complexes represent a promising opportunity for the design and development of novel bioactive molecules. These compounds display interesting antitumor activity and can be considered valid alternatives to platinum drugs, owing to their lower toxicity and stronger selectivity. 1 We report a systematic investigation of the interaction between arene ruthenium(ii) (arene = p-cymene, benzene or hexamethylbenzene) and natural bidentate ligands such as curcumin 2 () and quercetin 3 (Figure 2) that are bioavailable polyphenolic compounds well known for their antiinflammatory, antiviral, and antioxidant activity. 4 Figure 2 In the presence of anthracenyl moieties, no fluorescence emission was observed for complex 1 and 2. This can be ascribed to a photoinduced electron transfer process (PET) from the anthracene-localized first single excited state to the metal center. Here we report the synthesis and physico-chemical investigation on the two receptors. 2 [1] Credi A. ew J. Chem. 2012, 36, [2] Yafteh Mihan F., Bartocci S., Credi A., Silvi S., Dalla Cort A. Supramol. Chem. 2013, 25, Scheme 1 [1] Groessl, M.; Zava,.; Dyson, P. J. Metallomics 2011, 3, 591. [2] Caruso, F.; Rossi, M.; Benson, A.; pazo, C.; Freedman, D.; Monti, E.; Gariboldi, M. B.; Shaulky, J.; Marchetti, F.; Pettinari, R.; Pettinari, C. Journal of Medicinal Chemistry 2012, 55, [3] Lamson, D. W., Brignall, M. S. Alternative Medicine Review 2000, 5, 196. [4] Bonfili, L.; Pettinari, R.; Cuccioloni, M.; Cecarini, V.; Mozzicafreddo, M.; Angeletti, M.; Lupidi, G.; Marchetti, F.; Pettinari, C.; Eleuteri, A. M. ChemMedChem 2012, 7, 2010.
33 Poster 35 Hydrophilic Complexes of Pd(0) with Sugar-Derived Ligands: Synthesis, Characterization and Use in Catalysis Poster 36 Application of Sugar-Derived Phosphines in the Copper Catalyzed Asymmetric Conjugate Addition to Enones Giulia Tarantino* a, Matteo Lega a,b, Francesco Ruffo a,b, Maria Elena Cucciolito a,b Massimiliano Curcio,* Francesco Ruffo, Maria Elena Cucciolito, Matteo Lega a Dipartimento di Scienze Chimiche, Università di apoli Federico II, Italy; b Consorzio Interuniversitario di Reattività Chimica e Catalisi, Italy, Department of Chemical Sciences Paolo Corradini, University of aples FedericoII, Via Cinthia 21, aples, Italy; Palladium has an important role in catalysis due to the several reactions in which its complexes are used, such as C-C bond formation, e.g. Suzuki, Stille, Heck and Sonogashira couplings. In order to improve the sustainability of the reaction conditions, our work is focused on the synthesis of sugar-derived ligands, because the carbohydrates (i) are chiral, (ii) many of them are abundant in nature and (iii) can develop lypophilic or hydrophilic complexes according to the protection or deprotection of the hydroxyl groups. This work is focused on the synthesis of type 1 and type 2 hydrophilic complexes of Pd(0) (), containing,p- and,-bidentate ligands derived from D-mannose and D-glucose: The asymmetric conjugate addition () represents an useful method to afford new carbon-carbon bonds for the synthesis of enantiorich fine chemicals. 1 In the last years, a wide range of catalysts has been extensively studied, thus revealing the central role played by copper, as the metal center, 2 coordinated with phosphine ligands. 3 It should however be noted that there are still many issues to be clarified and improved with respect to this reaction, such as those related to improving the performance of the catalysts, the simplification of their synthesis, their easy recycle, the understanding of the mechanism. As part of our studies on the design of chiral ligands derived from sugars, we are currently preparing modular libraries of phosphines based on D- glucose, provided with different stereoelectronic motifs (Figure 2). Using bidentate ligands will allow the study of stability and reactivity of donor atoms with different π-acid property. The sugar residues (Hex), from common and easily available carbohydrates, can easily host the iminic function introduced in the positions 1, 2 or 6. The catalytic properties of the complexes will be verified in C-C bond formation reactions, especially Suzuki s cross-coupling reactions, with special attention towards the easy separation and reuse of the catalyst phase. [1] Johansson C.C.C. Seechurn, Kithching M., Colacot T.J., Snieckus V. Angew. Chem (51) [2] Benessere V., De Roma A., Del Litto R., Ruffo F. Coord. Chem. Rev (254) 390. Figure 2 Preliminary tests in the methylation of trans-3-nonen-2-one promoted by ZnMe 2 indicate that, in addition to the effects determined by the main coordinating functions, an important impact is played by the auxiliary functions present in the sugar backbone. [1] Kohei, E.; Daisuke, H.; Sayuri, Y.; Takanori, S.; Angew. Chem. Int. Ed. 2013, 52, [2] Christoffers, G.; Rosiak, A.; Synthesis, 2007, [3] Alexakis, A.; Bäckvall, J. E.; Krause,.; Pàmies,.; Diéguez, M.; Chem. Rev. 2008, 108, PSTERS
34 PSTERS Poster 37 Glucose-Derived Salen Ligands (Elpan-Salen) for the Manganese-Catalyzed Asymmetric Epoxidation of Styrenes Poster 38 A Supramolecular Peptide anofiber Templated Pd(0) anocatalyst For Efficient Suzuki Coupling Reactions Under Aqueous Conditions Alessandro Bismuto, a, * Maria E. Cucciolito, a,b Matteo Lega, a,b Francesco Ruffo, a.b Angela Tuzi a M. A. Khalily,*. Ustahuseyin, R. Garifullin, R. Genc, M. Guler a Dipartimento di Scienze Chimiche, Università di apoli Federico II, Italy; b Consorzio Interuniversitario di Reattività Chimica e Catalisi, Italy, Bilkent University, Institute of Materials Science and anotechnology, ational anotechnology Research Center (UAM), Ankara, TURKEY, 06800; The elpa-salen family of ligands 1 () is presented, which represents a subset of the elpa-type library based on D-glucose. 2 The ligands are structural analogues of the privileged salenh 2 derived from trans-1,2-diaminocyclohexane, 3 and differ for the position and the number of t-butyls in positions 3 and 5 of the aromatic portions. All of them, with the exception of elpa-salen-ah 2, show tactical t-bu groups in 3, i.e. ortho to the alcoholic oxygen. The activity of the Mn(III) complexes of the corresponding, -deprotonated chelates, [Mn(elpa-salen)]PF 6, has been assessed in the asymmetric epoxidation of cis- -methylstyrene, at 196 K in dichloromethane, by using metachloroperbenzoic (m-cpba) acid as the oxidant (scheme 1): R R 3 R 3 R 3 R 2 H H R 2 R 1 elpa-salen-ah 2 : R= R 1 = t-bu, R 2 = H, R 3 = Ac elpa-salen-bh 2 : R= R 1 = H, R 2 = t-bu, R 3 = Ac elpa-salen-ch 2 : R= R 1 = R 2 = t-bu, R 3 = Ac elpa-salen-dh 2 : R 1 = H, R= R 2 = t-bu, R 3 = Ac elpa-salen-eh 2 : R 1 = R 2 = t-bu, R= H, R 3 = Ac elpa-salen-c'h 2 : R= R 1 = R 2 = t-bu, R 3 = H Schene 1 The best performing catalyst, [Mn(elpa-salen-c)]PF 6, has then been examined in the epoxidation of other styrenes in the same conditions, substantiating the idea that appropriate functionalization of carbohydrates can produce effective ligands for enantioselective catalysis. 4 Self-assembly is an important technique for materials design using non-covalent interactions including hydrogen bonding, hydrophobic, electrostatic, metal-ligand, - and van der Waals interactions. 1 Various self-organized supramolecular nanostructures have been produced by using these non-covalent interactions. We explore use of peptide nanofibers formed by specially designed short peptide sequences that can form sheet-like hydrogen bonded structures for controlled synthesis of nanometer scale materials. In this work, we explored peptide nanostructures for their further utilization in catalysis and as a template in synthesis of inorganic nonmaterial s including inorganic catalysts. We fabricated Pd(0) nanostructures on the surface of self-assembled peptide nanofibers through mimicking biomineralization process. The Pd +2 salt was deposited and reduced on the surface of the preformed template. We observed that Pd(0) nanowire formation can be obtained in nanometer precision (). The Pd(0) catalyst were employed in model Suzuki coupling reactions. a) TEM image of the peptide nanofibers, b) SEM image of the peptide nanofiber network, c and d) TEM images of Pd nanoparticles on the peptide nanofibers Acknowledgements: This work is partially supported by grants; TUBITAK 109T603, TUBA-GEBIP, and FP7 Marie Curie IRG [1] Bismuto, A.; Carpentieri, A.; Cucciolito, M.E.; Lega, M.; Ruffo, F.; Tuzi, A. Inorg. Chim. Acta 2013, in print. [2] Benessere, V.; De Roma, A.; Del Litto, R.; Lega, M.; Ruffo, F. Eur. J. rg. Chem., 2011, 29, [3] Privileged Chiral Ligands and Catalysts, Zhou, Q.-L. Ed, Wiley-VCH Verlag GmbH & co.: Weinheim, [4] Benessere, V.; De Roma, A.; Del Litto, R.; Ruffo, F. Coord. Chem. Rev. 2010, 254, 390. [1] Hoeben, F. J. M.; Jonkheijm, P.; Meijer, E. W.; Schenning, A. Chem. Rev. 2005, 105,
35 Poster 39 Palladium complexes as catalysts for synthesis of amines Poster 40 Use of Diethylaminodifluorosulfinium Salt for the Fluorination of Phosphorus xyacids Agnieszka Krogul,* Katarzyna Jakacka, Grzegorz Litwinienko University of Warsaw, Faculty of Chemistry, Pasteura 1, Warsaw, Poland, Fuencisla Delgado, a * Vincenzo Mirabello, a,c Kolio Raltchev, b Konstantin Karaghiosoff, b Maria Caporali, a Luca Gonsalvi, a Werner berhauser, a Maurizio Peruzzini a a ICCM-CR, Via Madonna del Piano 10, Sesto Fiorentino, Firenze, Italy; b Department Chemie und Biochemie, Ludwig-Maximilians Palladium(II) complexes with nitrogen donor ligands have received much attention. These complexes can be applied as catalysts for the carbonylations, 1,2 polymerizations, 3 and other reactions in synthetic organic chemistry. 4 There is a general agreement that catalytic activity of Pd(II) complexes with nitrogen containing ligands depends on electron density on the palladium atom and a strategy to design (and to obtain) more active catalysts is based on incorporation of new ligands to manipulate the steric and electronic effects around the palladium center. In the present study X-ray characterization and thermal analyses were applied in order to investigate substituent effects on the crystal structures and stability of PdCl 2(X npy) 2 complexes (where: Py = pyridine; X = Cl or Me; n = 0-2). Electrondonating properties of X npy ligands were described by determined experimentally acidity parameter, pk a. btained results were combined with catalytic activity of PdCl 2(X npy) 2 in the reduction of nitrocompounds to amines by the use of C/H 2 (scheme 1): Scheme 1 Universitaet Muenchen, Butenandtstrasse 5, Muenchen, Germany; c Current address: Department of Chemistry, University of Bath, Claverton Down, Bath, UK, BA2 7AY; Among the various useful protocols for the introduction of fluorine into organic molecules, electrophilic fluorination is a promising and exciting area of research. Recently, a variety of electrophilic fluorinating reagents has been prepared 1 such as DAST (diethylaminosulfur trifluoride), Deoxo-Fluor, (bis(2-methoxyethyl)aminosulfur trifluoride) and Selectfluor (1- chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)). Moreover, dialkylaminodifluorosulfinium salts have shown to be efficient deoxofluorinating agents for the transformation of a wide range of organic compounds, such as alcohols, ketones, aldehydes and acyl chlorides into the corresponding fluorides, having the advantage of high stability and easy handling. 2 This work presents the use of diethylaminodifluorosulfinium tetrafluoroborate, XtalFluor-E, for the first time in the transformation of phosphorus oxyacids as H 3P 2, H 3P 3 and PhP()(H)(H) into fluorophosphine ligands. The procedure works well in the presence of an unsaturated ruthenium organometallic complex, which stabilizes the pyramidal tautomer 3 of the P-oxyacids i.e. P(H) 2(R), [R = H, Ph, H] which are prone to react with XtalFluor-E. (Scheme 1) Reduction of nitrocompounds to amines by the use of carbon monoxide is an alternative method for the hydrogenation of nitrocompounds and it allows to eliminate very expensive hydrogen (which is involved in the synthesis of amines nowadays). We report that nature and position of substituent in the aromatic ring is important to the structure of PdCl 2(X npy) 2 complexes, however, we did not find a direct correlation between basicity of ligand and the Pd- distance. Moreover, complexes with methylpyridines are more thermally stable than their analogues with chloropyridines. Thermal stability of PdCl 2(X npy) 2 complexes is correlated with their catalytic activity in reduction of nitrocompounds to amines by the use of C/H 2. We observed an increase of reaction rate with decreasing basicity of X npy ligand in the reduction of nitrocompounds. For complexes with ortho substituted pyridines significantly lower conversions were observed. n the basis of presented data we propose mechanism of investigated process. [1] mae, I. Coord. Chem. Rev. 2011, 255, 139. [2] Krogul, A.; Skupińska, J.; Litwinienko, G. J. Mol. Catal. A 2011, 337, 9. [3] wen, G. R.; Burkill, H. A.; Vilar, R.; White, A. J. P.; Williams,D. J. J. rganomet. Chem. 2005, 690, [4] Gil-Molto, J.; ajera, C. Eur. J. rg. Chem. 2005, 19, Scheme 1 [1] a) Shimizu, M.; Hiyama, T. Angew. Chem. Int. Ed. 2005, 44, b) yffeler P.T.; Gonzalez Durón, S.; Burkart, M.D., Vicent, S.P.; Wong, C.-H. et al. Angew. Chem. Int. Ed. 2005, 44, [2] L Heureux, A.; Beaulieu, F.; Bennett, C.; Bill, D.R.; Clayton, S.; LaFlamme, F.; Mirmehrabi, M.; Tadayon, S.; Tovell, D.; Couturier, M. J. rg. Chem. 2010, 75, and references therein. [3] a) Akbayeva, D.; Di Vaira, M.; Constantini, S.S.; Peruzzini, M.; Stoppioni, P. Dalton Trans., 2006, b) Manca, G.; Caporali, M.; Ienco, A.; Mealli, C.; Peruzzini, M. submitted. PSTERS
36 PSTERS Poster 41 Metathesis Reaction for the Synthesis of Macrocyclic Drug Compounds: Benefits of anofiltration Technology for Greener Large Scale Production Anna Cupani,* a Dominic rmerod, b Andras Horvath, a Andrew G. Livingston c Poster 42 Tetrathia[7]helicene Phosphane Derivatives: Properties and Characterization Davide Dova,* a Silvia Cauteruccio, a Lucia Viglianti, a Claudia Graiff, b Patrizia R. Mussini, a Emanuela Licandro a a Janssen Pharmaceutica V, Beerse, Belgium, b VIT, Mol, Belgium, c Imperial College, London, UK. a Dipartimento di Chimica, Università degli Studi di Milano, Via C. Golgi 19, Milano, Italy; b Dipartimento di Chimica, Università degli Studi di Parma, Viale delle Scienze 17/A, Parma, Italy; Macrocycles are currently used as Active Pharmaceutical Ingredients (API) in a large number of applications 1. Compared to their linear equivalent, they are less prone to proteolysis, exhibiting a longer half-life and an improved pharmaceutical activity 2. Ring Closing Metathesis (RCM) can be of great use in the synthesis of such compounds 3. Since the pioneering works from Grubbs and co-workers on olefins metathesis, extensive investigations have been done, leading to a better mechanistic understanding and to the development of efficient catalysts for demanding substrates 4. We report about a real industrial case where olefin metathesis can be successfully used in the synthesis of TMC435, a complex macrocyclic API for hepatitis C treatment (figure 1). Tetrathia[7]helicenes (7-TH) are polyconjugated π-systems in which four thiophene rings are orthofused to alternating arene rings to generate a non-planar, chiral, stable helix, allowing the existence of M and P enantiomers. 1 In the course of our studies on the synthesis of 7-TH phosphorus derivatives as potential innovative chiral ligands in asymmetric organometallic catalysis, 2 novel 7-TH-dialkylsubstituted phosphane derivatives 1 and 2 () have been synthesized and fully characterized. Chiroptical properties of borane adducts 1 have been investigated along with the electrochemical properties of phosphine ligands 2 (). S H H S Me. TMC435, API used in the treatment of hepatitis C. The synthesis of macrocycles is heavily dependent on the dilution conditions: the more diluted a mixture, the higher the ratio between intra- and inter-molecular reactions. rganic Solvent anofiltration (S) is an attractive technology because, through a separation on a molecular scale and under relatively mild conditions, it allows the isolation and purification of the products and the recovery and recycle of the by-products and the solvent 5. In our work we aim at coupling it with the metathesis reactions to develop a more sustainable process. [1] Li, P.; Roller, P.P; Xu, J. Current rganic Chemistry, 2002, 6(5), [2] Marsault, E.; Peterson, M. L. Journal of medicinal chemistry, 2011, 54(7), [3] Gradillas, A.; Perez-Castells, J.; Angewandte Chemie Int. Ed, 2006, 45, [4] Clavier, H.; Grela, K.; Kirshning, A.; Mauduit, M.; olan, S. P.; Angew. Chem. Int. Ed. 2007, 46, [5] Geens, J., De Witte B., Van der Bruggen B. Separation Science and Technology, 2007, 42(11), [1] Collins, S. K.; Vachon, M. P. rg. Biomol. Chem. 2006, 4, [2] a) Cauteruccio, S.; Loos, A.; Bossi, A.; Blanco Jaimes, M. C.; Dova, D.; Rominger, F.; Prager, S.; Dreuw, A.; Licandro, E.; A. S. K. Hashmi A. S. K. Inorg. Chem in press. b) Monteforte, M.; Cauteruccio, S.; Maiorana, S.; Benincori, T.; Forni, A.; Raimondi, L.; Graiff, C.; Tiripicchio, A.; Stephenson, G. R.; Licandro, E. Eur. J. rg. Chem. 2011,
37 Poster 43 Dinuclear Arene Ruthenium(II) Complexes with 3,3,5,5 -Tetramethyl-4,4 -Bipyrazole and Modulation of Proteasome Activity Poster 44 ne-pot Gold-Catalyzed Aminofluorination of Unprotected 2-Alkynylanilines Aurel Tabacaru, a ertil Xhaferaj, b * Riccardo Pettinari, a Fabio Marchetti, b Claudio Pettinari, a Massimiliano Cuccioloni, c Anna Maria Eleuteri c a School of Pharmacy, Via S. Agostino 1, Camerino (MC), Italy; b School of Science and Technology, Via S. Agostino 1, Camerino (MC), Italy; c School of Biosciences and Biotechnology, Via Gentile III da Varano, Camerino (MC), Italy; During the last decades, the preparation of half-sandwich ruthenium(ii) complexes incorporating systems has registered a growing attention, especially due to their potentiality as metallo-pharmaceuticals 1 as well as catalyst in synthetic organic chemistry. 2 In the present work, a series of dinuclear arene ruthenium(ii) complexes coordinated by the ditopic -ligand 3,3,5,5 -tetramethyl-4,4 -bipyrazole (H 2Me 4BPZ) have been prepared (Scheme 1), and preliminary results regarding their ability to modulate proteasome activity are reported. MeH [Ru(Arene)Cl 2 ] 2 + H 2 Me 4 BPZ r.t., 2 h H Cl Arene Ru Cl H Cl Arene Ru Cl Antonio Arcadi, a Emanuela Pietropaolo, a Antonello Alvino, b Veronique Michelet c a Dipartimento di Scienze Fisiche e Chimiche, Università di L Aquila, Via Vetoio Coppito(AQ), Italy; b Dipartimento di Chimica, Sapienza, Università di Roma, P. le A. Moro 5, Roma, Italy; c Chimie ParisTech, Laboratoire Charles Friedel, UMR 7223, 11 rue P. et M. Curie, Paris Cedex 05, France Introducing fluorine into molecules represents a major challenge in organic synthesis. 1 The substitution of hydrogen with fluorine can lead to a dramatic impact in the physicochemical and biological properties of organic compounds, and utilization of fluorine derivatives spans areas as diverse as pharmaceuticals, agrochemicals and polymers. 2 In recent years it has been synthesized a class of stable and easily manipulated fluorinating reagents to which belongs the Selectfluor. 3 In this work we combine the characteristics of Lewis acid / transition metal of gold, capable of catalyzing the sequential ammination / annulation reaction of the substrate A, 4 with the fluorinating activity of Selectfluor to obtain the C3 fluorinated indole derivatives according to the scheme 1: Arene = p-cymene 1 hexamethylbenzene 2 benzene 3 Scheme 1 [1] a) Ang, W. H., Dyson, P. J. Eur. J. Inorg. Chem. 2006, 19, 4003; b) Casini, A., Gabbiani, C., Sorrentino, F., Rigobello, M. P., Bindoli, A., Geldbach, T. J., Marrone, A., Re,., Hartinger, C. G., Dyson, P. J., Messori, L. J. Med. Chem. 2008, 51, 6773; c) Pettinari, R., Pettinari, C., Marchetti, F., Clavel, C. M., Scopelliti, R., Dyson, P. J., rganometallics 2013, 32, 309. [2] a) icks, F., Aznar, R., Sainz, D., Muller, G., Demonceau, A. Eur. J. rg. Chem. 2009, 29, 5020; b) Pettinari, C.; Marchetti, F.; Cerquetella, A.; Pettinari, R.; Monari, M.; Mac Leod, T. C., Martins, L. M. D. R. S., Pombeiro, A. J. L. rganometallics 2011, 30, 1616; c) Schinkel, M., Marek, I., Ackermann, L. Angew. Chem. 2013, 52, Scheme 1 Depending on the nature of the substituent groups R 1 and R 2 is possible to obtain the final products by operating either through a domino process or through a one-pot/two-steps type process, in which the addition of Selectfluor occurs after the complete annulation of the substrate A. Furthermore it is possible, by modulation of the stoichiometric ratio between Selectfluor and starting material, to obtain both C3 difluorinated and C3 monofluorinated products. [1] Kirsch, P. Modern Fluoroorganic Chemistry: Synthesis Reactivity Applications; Wiley-VCH: Weinheim, [2] (a) Gouverneur, V. Science 2009, 325, (b) Zhang, W.; Cai, Ch. Chem. Commun. 2008, (c) Hagan, D. Chem. Soc. Rev. 2008, 37, [3] yffeler, P. T.; Durn, S. G.; Burkart, M. D.; Vincent, S. P.; Wong, C. H. Angew. Chem. Int. Ed., 2005, 44, ; [4] Arcadi, A.; Bianchi, G.; Marinelli, F. Synthesis, 2004, 4, PSTERS
38 PSTERS Poster 45 Squaramides as Potent Transmembrane Anion Transporters 1 Poster 46 Ligand Induced Structural and Electronic Variations in Multimetallic Complexes. Busschaert,* a I. L. Kirby, a S. Young, a M. E. Light, a P. Hornton, a P. A. Gale a Phillip Wright a, Sara Muzzioli b, Paolo Raiteri a, Stefano Stagni b, Max Massi a a School of Chemistry, University of Southampton, Southampton, S17 1BJ, U.K., a Department of Chemistry, Curtin University, Kent Street, Bentley WA 6102, Australia; b Department of Physical and Inorganic Chemistry, University of Bologna, viale del Risorgimento, I Bologna, Italy The transport of anions across cellular membranes is an important biological process that is controlled by specialized membrane proteins. Malfunctioning of these proteins has been linked to a variety of diseases, most notably cystic fibrosis. 2 Therefore, there has been an interest in developing synthetic membrane transporters that can substitute these proteins. A large part of these synthetic mobile anion carriers contain urea or thiourea functionalities in their anion binding site. However, there has been a recent interest in the field of medicinal chemistry to use squaramide derivatives as isosteres for ureas and guandinium groups, since it is believed that the stability of bis-squaramides to nucleophilic attack can reduce their in vivo toxicity. 3 In addition, squaramides are being increasingly used by supramolecular chemists in the design of ion receptors. 4 We therefore decided to investigate the anion binding and transmembrane anion transport properties of a series of symmetrical fluorinated squaramides and their analogous ureas and thioureas. Squaramides were prepared by the Zn(Tf) 2 catalysed reaction between diethoxy squarate and the appropriate aniline. A series of vesicle-based experiments revealed that the squaramide containing compounds are significantly better at transporting anions across a lipid bilayer than the more traditional urea and thiourea derivatives. This behaviour could be rationalized by the superior anion binding properties that were found for these squaramides through MR titration techniques and X-ray structure determination. Furthermore, it was also shown that the fluorinated squaramides displayed higher transport abilities at much lower concentration compared to the unfluorinated receptors. Both findings promise new guidelines for the design of future anion transporters and transport related drugs. [1]. Busschaert, I. L. Kirby, S. Young, M. E. Light, P. Horton, P. A. Gale, Angew. Chem. Int. Ed. 2012, 51, [2] F. M. Ashcroft, Ion Channels and Disease, Academic Press, San Diego - London, [3] R. I. Storer, C. Aciro, L. H. Jones, Chem. Soc. Rev. 2011, 40, [4] (a) V. Amendola, G. Bergamaschi, M. Boiocchi, L. Fabbrizzi, M. Milani, Chem.-Eur. J. 2010, 16, (b) A. Rostami, A. Colin, X. Y. Li, M. G. Chudzinski, A. J. Lough, M. S. Taylor, J. rg. Chem. 2010, 75, rganometallic rhenium(i) complexes exhibiting phosphorescence have been of interest due to their potential application in fields such as biological imaging, light emitting devices, sensors, and catalysis. 1 Recent investigations have shown that the inclusion of a tetrazole ligand can have a significant effect on the structural and photophysical character of luminescent compounds, and can behave as an effective bridging ligand between multiple metal centres allowing efficient energy transfer. 2 We have previously reported the chemistry and photophysical nature of mononuclear and homo-dinuclear rhenium tetrazole compounds. 2,3 Here we extend the investigation of the versatile nature of the tetrazole ligand to multinuclear and hetero-dinuclear compounds (). 3,4 [1] Kirgan, A.; Sullivan, R.; Rillema, P. Top. Curr. Chem. 2007, 45. [2] Wright, P. J.; Muzzioli, S.; Werrett, M. V.; Raiteri, P.; Skelton, B. W.; Silvester, D. S.; Stagni, S.; Massi, M. rganometallics. 2012, [3] Wright, P. J.; Muzzioli, S.; Skelton, B. W.; Raiteri, P.; Lee, J.; Koutsantonis, G.; Silvester, D. S.; Stagni, S.; Massi, M. Dalton T. 2013, [4] Wright, P. J.; Affleck, M. G.; Muzzioli, S.; Skelton, B. W.; Raiteri, P.; Silvester, D. S.; Stagni, S.; Massi, M. rganometallics. 2013, In Press.
39 Poster 47 Silver(I) Acylpyrazolonate Complexes Embedded in Polyethylene with Potent Antibacterial Activity Jessica Palmucci, a * Stefania Scuri, b Mirko Marangoni, c Francesca Condello, a Serena rbisaglia, a Fabio Marchetti, a Claudio Pettinari b Poster 48 ew Cooperative Ligands for C-H Bond Activations Reactions Sandra Y. de Boer,* Joost. H. Reek, Jarl Ivar van der Vlugt* Homogeneous, Supramolecular & Bio-Inspired Catalysis Group, van t Hoff Institute for Molecular Sciences, University of Amsterdam, P. Box 94720, 1090 GS Amsterdam, The etherlands, a School of Science and Technology, Via S. Agostino 1, Camerino (MC), Italy; b School of Pharmacy, Via S. Agostino 1, Camerino (MC), Italy; c Analisi Control S.r.l., Via San Claudio 5, Corridonia (MC). Silver ions and its compounds are known to exhibit strong antimicrobial activity towards broad-spectrum bacteria. [1] Silver nanoparticles (Ps) embedded in polymeric matrix have proven to prevent the adherence and proliferation activities of the bacteria at surface of polymeric materials [2] through an efficient Ag + release from the surface and direct interactions with the bacterial cell wall. However, an extensive release of the Ag Ps from the materials could lead to environmental hazard. [3,4] Following our previous research on this topic, [5] here we report some novel complexes of silver(i) containing 4-acyl-5- pyrazolonate ligands with different electronic and steric features and several imidazoles L as ancillary ligands (). Their structure have been confirmed by analytical and spectral data (IR, 1 H-MR, 13 C-MR, ESI-MS, Elem. Anal.) and X- ray diffraction studies. Specific tests were carried out on all derivatives embedded in polyethylene disks to probe their antimicrobial activity against suspensions of E. coli, P. aeruginosa and S. aureus, but without evident Ag + release. Antimicrobial action on contact is under investigation. In biological systems, cooperativity between metal and ligands is often employed to mediate proton transfer and redox reactions or substrate activation. Inspired by the versatile application observed in nature, metal-ligand bifunctional catalysts were recently demonstrated to be also useful in a series of activation reactions and catalytic conversions, 1-3 where traditionally chemical reactions are solely metal-mediated. The respective smart ligand systems typically cooperate in substrate binding and activation through secondary interactions like redox non-innocence or proton transfer. Thus, the adaptive ligand can now work as an internal base and this would be a new development in the search of new catalytic routes for functionalization reactions. ne of these functionalization reactions is the catalytic carboxylation reaction which comprises the insertion of C 2 into C-H bonds, obtaining carboxylic acids as products. 4 This reaction, which uses C 2 as a C1 building block, is still one of the dream reactions of catalysis, because carbon dioxide is abundant and non-toxic and carboxylic acids are attractive for natural and medicinal compounds. Here we demonstrate various versatile ligands that are able to operate in a cooperative manner when combined to several late TMs.[5,6] Furthermore, we will discuss studies of these new cooperative complexes [7] towards the activation of C-H bonds. The thus formed metal-carbon bond may then undergo reactions with other substrates to enforce coupling (C- C bond) reactions such as the highlighted carboxylation reactions, but also cross (dehydrogenative) coupling (CDC) or hydroaddition reactions. [1] Tamboli, M. S.; Kulkarni, M. V. Biointerfaces 2012, 92, [2] Kar, S.; Subramanian, M.; Ghosh, A. K.; Desalination and water treatment 2011, 27, [3] Gordon,.; Slenters, T. V.; Brunetto, P. S.; Antimicrob. Agents Chemother. 2010, 54, [4] Helttunen, K.; Moridi,.; Shahgaldian, P.; issinen, M. rg. Biomol. Chem. 2012, 10, [5] Tăbăcaru, A.; Pettinari, C.; Marchetti,F.; Di icola,c.; Domasevitch, K. V.; Galli, S.; Masciocchi,.; Scuri, S.; Grappasonni, I.; Cocchioni, M. Inorg. Chem. 2012, 51, [1] Zhang, J.; Leitus, G.; Ben-David, Y.; Milstein, D. J. Am. Chem. Soc. 2005, 127, [2] Kashiwame, Y.; Kuwata, S.; Ikariya, T., Chem. Eur. J. 2010, 16, 766. [3] Fujita, K.; Tanino,.; Yamaguchi, R. rg. Lett. 2007, 9, 109. [4] stapowicz, T.G.; Hölscher, M.; Leitner, W., Chem. Eur. J. 2011, 17, [5] de Boer, S. Y.; Gloaguen, Y.; Lutz, M.; van der Vlugt, J. I., Inorg. Chim. Acta 2012, 380, 336. [6] van der Vlugt, J. I., Eur. J. Inorg. Chem. 2012, 3, 363. [7] de Boer, S.Y.; Gloaguen, Y.; Reek, J.H.; Lutz, M.; van der Vlugt, J.I., Dalton Trans. 2012, 3, PSTERS
40 PSTERS Poster 49 Influence of η 6 -Arene Ligand on Asymmetric Transfer Hydrogenation of Imines Petr Šot, a * Beáta Vilhanová, a Jan Pecháček, a Jiří Václavík, a Jakub Januščák, a Marek Kuzma, b Petr Kačer a a Department of rganic Technology, Institute of Chemical Technology, Technická 5, Prague 6, Czech Republic; b Laboratory of Molecular Structure Characterization, Institute of Microbiology, v.v.i.; Academy of Sciences of the Czech Republic, Vídeňská 1083, Prague 4, Czech Republic; During the last fifteen years, the asymmetric tranfer hydrogenation (ATH) of prochiral imines and ketones via oyori s piano-stool complexes [RuCl(S,S)-(TsDPE)(η 6 -arene)] (TsDPE = -(p-toluenesulfonyl)-1,2-diphenylethylene-1,2- diamine) has become a user-friendly and relatively well-understood procedure for the preparation of enantiomerically pure amines and alcohols. Yet, up to date, no study has clarified the influence of the η 6 -ligand s structure on imine ATH despite the existence of at least four commercially available modifications. Analogous studies exist only for ketones, nevertheless, the ketone pathway strinkingly differs from the imine one. ur study clearly conludes that reaction rate, enantioselectivity and even solubility is strongly dependent on substitution of the η 6 -arene: e.g. in the case of a catalyst with hexamethylbenzene as the η 6 -ligand, the reaction proceeds only very slowly, and in cases of ATH of 1-phenyl-substituted dihydroidoquinolines via catalyst with benzene as the η 6 -ligand enantioselectivity was close to zero. Studying these modifications can help us to better understand structure-activity relationships and thus help to develop catalytical systems with better properties. Poster 50 Synthesis of itrogen-containing Heterocycles via Ring-Closing Ene-Ene and Ene-Yne Metathesis Reactions Gabriella Ieronimo,* Erica Benedetti, Andrea Penoni, Giovanni Palmisano a Dipartimento di Scienza e Alta Tecnologia, Università degli Studi dell Insubria, via Valleggio 11, 22100, Como, Italy. In the last few years ring-closing ene-ene metathesis and ring-closing ene-yne metathesis emerged as a versatile synthetic technique to obtain medium-sized carbo- and heterocycles as well as natural products. 1,2,3 We recently developed a regioselective ring-closing metathesis approach to the synthesis of highly functionalizable 1- benzazepine and 2-benzazepine scaffolds and five- and six- membered lactams using the second generation Hoveyda- Grubbs catalyst. 4 The synthetic strategy started from compound 1 and 2 (n = 1) to afford respectively 1-benzazepine and 2- benzazepine ring (scheme 1). By changing the alkyl chain an approach to the preparation of large ring nitrogen-containing heterocycles was studied. n catalyst (3 mol%) toluene, 2 70 C, 2h (0.05 M) n 1 (n = 1-5) n catalyst (3 mol%) toluene, 2 70 C, 2h (0.02 M) n 2 (n = 1-5) Scheme 1 Acknowledgement: This work has been financially supported by the Grant Agency of the Czech Republic (Grant GACR P106/12/1276), and by grant for long-term conceptual development of Institute of Microbiology RV: [1] Fürstner. A. Chem. Commun. 2011, 47, [2] Tamesova, M.; Sturla, S. J. Chem. Rev. 2012, 112, [3] Mutlu, H.; De Espinosa, L. M. ; Meier, M. A. R. Chem. Soc. Rev. 2011, 40, [4] Benedetti, E.; Lomazzi, M.; Tibiletti, F.; Goddard, J. P.; Fensterbank, L.; Malacria, M.; Palmisano, G.; Penoni, A. Synthesis, 2012, 44, 3523.
41 Poster 51 Bio-derived Chemicals and Fuels: a scientific partnership between Venice and Sydney Alessio Caretto, a,b * Alvise Perosa a a Department of Molecular Sciences and anosystems, Centre for Sustainable Technology, Università Ca Foscari, Dorsoduro, Venezia, Italy; b Laboratory of Advanced Catalysis for Sustainability, School of Chemistry, building F11, The University of Sydney, 2007, Australia; The PhD cotutelle scheme between Venice and Sydney has allowed to couple research on green transformations of biobased chemicals (including conversion mechanisms from platforms to their derivatives), with catalysts and processes for the improvement of bio-fuels (e.g. derived from algal feedstocks and by new technologies from lignocelluloses). Bio-based chemicals in Venice. In Venice, the reactivity of bio-based platform chemicals such as levulinic acid and C 4- C 5 lactones, 1,2 with organic carbonates, 3,4 has been studied. This was done with a view of obtaining higher value added chemical compounds 5 by new greener broad-based chemical technologies. 6 Bio-fuels in Sydney. In Sydney, on-water catalysis was applied to reduce the cloud point of biodiesel (the temperature at which crystals start to form in the fuel). This green innovative methodology was employed to carry out cycloadditions between fatty acids, constituents of biodiesel, and opportune bioderived dienes or dienophiles. Poster 52 Design and Synthesis of ew Zinc-Salophen Complexes as Receptors for Biologically Relevant Anions Martina Piccinno, a * Francesco Yafteh Mihan, a Gianpiero Forte, a Antonella Dalla Cort, a Gemma Aragay, b Pablo Ballester b,c a Università Sapienza, Piazzale Aldo Moro, 5, Roma (RM), Italy; b Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, Tarragona, Spain; c Catalan Institution of Research and Advanced Studies (ICREA), Passeig Lluís Companys 23, Barcelona, Spain; In the recent years, many studies have been focused on the development of synthetic molecular receptors for biologically relevant anions. 1 Among all, phosphates have received considerable attention due to their crucial role in life processes. In particular, nucleotides such as ATP, ADP and AMP are considered the most important due to their implication in energy transfer and storage in living cells. 2 Fluorescent and colorimetric based chemosensors represent useful tools owing the simplicity of the instrumentation and the high sensitivity of their optical response. In this field, zinc-salophen complexes have been widely exploited in anion recognition, and more concretely for phosphate. 3 In this work, we report the synthesis of a new zinc-salophen derivative (sal 1, ) and we show preliminary 1 H-MR spectroscopic studies of its binding affinity towards some anions. Transformation of chemicals and fuels obtained from biomass. [1] Corma, A.; Iborra, S.; Velty, A. Chem. Rev. 2007, 107, [2] Werpy, T.; Petersen, G. Top Value Added Chemicals from Biomass, U.S. D.E [3] Selva, M.; Perosa, A. Green Chem. 2008, 10, [4] Selva, M.; Marquez, C. A.; Tundo, P. Gaz. Chim. It. 1993, 123, [5] Caretto, A.; Perosa, A. Sust. Chem. Eng. 2013, ASAP (DI: /sc400067s). [6] Bozell, J. J.; Petersen, G. R. Green Chem. 2010, 12, Unfortunately, Sal 1 shows poor solubility in most of the typical organic solvents (e.g. CHCl 3, CH 2Cl 2, THF). However, it is highly soluble in DMS what makes the binding of guests a real challenge. Thus, to increase the solubility of the receptor in common, non-competitive organic solvents we are currently involved in the modification on the skeleton of sal 1. [1] Zhou, Y.; Xu, Z.; Yoon, J. Chem. Soc. Rev. 2011, 40, [2] Rao, A. S.; Kim, D.; am, H.; Jo, H.; Kim, K. H.; Ban, C.; Ahn, K. H. Chem. Commun. 2012, 48, [3] Cano, M.; Rodriguez, L.; Lima, C.; Pina, F.; Dalla Cort, A.; Pasquini, C.; Schiaffino, L. Inorg. Chem. 2009, 48, PSTERS
42 PSTERS Poster 53 xidative Addition to Cyclometalated Complexes of Pt(II) Poster 54 Hydrogen Bond-Induced Assembly of Supramolecular Bidentate,- and,p-ligands Luca Maidich, a,b * Jonathan P. Rourke, b Sergio Stoccoro, a Antonio Zucca a Eleonora Russotto, a,b * Marco Durini, a Joost Reek, b Umberto Piarulli a a Dipartimento di Chimica e Farmacia, Università di Sassari, Via Vienna 2, Sassari (SS), Italy,; b Department of Chemistry, University of Warwick, CV4 7AL Coventry, United Kingdom; a Università dell Insubria, Dipartimento di Scienza e Alta Tecnologia, via Valleggio 11, Como, Italy; b Universiteit van Amsterdam, HIMS, Science Park 904, 1098 XH Amsterdam, The etherlands; Cyclometalated complexes have been studied in depth and almost every d-block transition metal has its own representative; partly this is because cyclometalation reactions are envisaged as intramolecular analogues of intermolecular C-H activation/functionalization in solution 1 and in gas phase. 2 Rollover cyclometalation is a particular type of C-H activation that involves ligands with at least one heteroatom (usually belonging to group 15 or 16) as donor in order to assist the activation of the relatively inert C-H bond. Among the wide reactivity offered by Pt(II) cyclometalated complexes is the two electron oxidation to Pt(IV) which opens up a parallel world of possibilities. The importance of the oxidized complexes is well documented in many different fields: from functionalization of saturated and unsaturated hydrocarbons to material science and medicinal chemistry. ur interest in these species is related both to synthesis 3 and reactivity. 4 Here we use CH 3I as oxidizing agent with some cyclometalated complexes of substituted 2-phenylpyridines and 2,2 -bipyridines. The differences in reactivity are striking showing that electronic properties of the coligands are of paramount importance in stabilizing the oxidized metal centre. Pt(IV) rollover complexes, moreover, offer a promising type of chemistry because permit to achieve a rather rare C(sp 3 )- C(sp 2 ) coupling which is still under investigation. 5 In recent years, combinatorial and supramolecular approaches to the development of new ligands for asymmetric catalysis have gained momentum. 1 Supramolecular ligands contain, besides the atom(s) coordinating to the catalytic metal, an additional functionality capable of non-covalent interactions which can play the following roles: 1) allowing two monondentate ligands to self-assemble into the so-called supramolecular bidentate ligands ; 2) binding the substrate(s) in proximity to the catalytic metal center, in analogy to metalloenzymes. In both cases, this approach causes reduced degrees of freedom in the metal coordination complexes, which are thus expected to result in more pre-organized systems with a better capacity of controlling the metal-catalyzed reaction. In the last few years, several powerful supramolecular bidentate ligands with outstanding reactivity and selectivity have been described, but unfortunately, this concept has so far been exclusively confined to the use of phosphorus ligands. 1 We report herein the first example of hydrogen bond-induced assembly of monodentate oxazolines for the formation of supramolecular bis(oxazoline) (SupraBox) ligands () and their application in the copper(ii) catalyzed asymmetric acylation of diols.2 In addition we describe also the synthesis of the first supramolecular phosphinoxazoline transition metal complexes (Figure 2). Figure 2 [1] (a) Shibata, T.; Takayasu, S.; Yuzawa, S.; tani, T. rg. Lett., 2012, 14, (b) Kwak, J.; hk, Y.; Jung, Y.; Chang, S. J. Am. Chem. Soc., 2012, 134, [2] Butschke, B.; Schwarz, H. Chem. Sci., 2012, 3, [3] See for example (a) Petretto, G. L.; Rourke, J. P.; Maidich, L.; Stoccoro, S.; Cinellu, M. A.; Minghetti, G.; Clarkson, G. J.; Zucca, A. rganometallics, 2012, 31, (b) Zucca, A.; Stoccoro, S.; Cinellu, M. A.; Petretto, G. L.; Minghetti, G. rganometallics, 2007, 26, [4] See for example (a) Crosby, S. H.; Thomas, H. R.; Clarkson, G. J.; Rourke, J. P. Chem. Commun., 2012, 48, (b) Maidich, L.; Zucca, A.; Clarkson, G. J.; Rourke, J. P. rganometallics, 2013, 32, [5] Zucca, A., et al., manuscript in preparation. A small library of bifuntional oxazoline ligands was prepared using differently substituted oxazoline nuclei, linkers and different urea substituents. The formation of the transition metal complexes (Cu 2+, Pd 2+ and Ir + ) was investigated by MS, UV/Vis and MR spectroscopy. The SupraBox library was screened in the copper-catalyzed asymmetric benzoylation of vic-diols. Good selectivities were obtained in the kinetic resolution of racemic hydrobenzoin [up to 86%ee and selectivity (s) = 28] and in the desymmetrization of meso-hydrobenzoin (up to 88%ee). [1] Carboni, S.; Gennari, C.; Pignataro, L.; Piarulli, U. Dalton Trans. 2011, 40, [2] Durini, M.; Russotto, E.; Pignataro, L.; Reiser,.; Piarulli, U. Eur. J. rg. Chem. 2012, 5451.
43 Poster 55 ew Supramolecular Structures Based on Au(I) Luminescent Hydrogels Poster 56 Gold(I) Complexes Targeting TrxR Enzyme as Anticancer Drugs E. Aguiló, a * R. Gavara, b J. Llorca, c J. C. Lima, b L. Rodríguez a J. Arcau, a * V. Andermark, b M. Rodrigues, c L. Pérez-García, c I. tt, b L. Rodríguez a a Dept. de Química Inorgànica, Universitat de Barcelona, Barcelona, Spain; b REQUIMETE, Dept. de Química, CQFB, Universidade ova de Lisboa, Monte de Caparica, Portugal; c Institut de Tècniques Energètiques i Centre de Recerca en anoenginyeria, U.P.C., Barcelona, Spain; a Departament de Química Inorgànica, Facultat de Química, Universitat de Barcelona, Barcelona, Spain; b Institute of Medicinal and Pharmaceutical Chemistry, Technische Universität Braunschweig, Braunschweig, Germany; c Laboratori de Química rgànica, Facultat de Farmàcia, and Institut de anociència i anotecnologia, Universitat de Barcelona, Barcelona, Spain; Gels are an outstanding group of soft materials lying at the interface of solid and liquid, and find numerous applications in various fields including tissue engineering, biosensors, food processing, cosmetics, photography, controlled drug delivery etc. Amongst the variety of gels, hydrogels (those that entrap water) are of special importance owing to their tremendous potential in biomedicine and supramolecular chemistry. Moreover, gold(i) complexes exhibit interesting self-assembly properties that usually are modulated by the presence of aurophilic (Au Au) interactions. 1 It has been very recently found that the [Au(4-ethynylpyridyl)(phosphine)] (phosphine = PTA, DAPTA) organometallic complexes forms hydrogels 2,3 and this fact opens a new and promising research field related metallohydrogels obtained with very simple chemical structures. The small variation on the phosphine structure (DAPTA instead of PTA) (Fig. 1a) has observed to affect the observed properties: i) a great increase on the hydrogel entanglement structure has been observed; ii) the different cross-linking structures give rise to specific emission properties. In this work, we also present how can affect the introduction of different alkylic length chains attached to the PTA phosphine (Fig. 1b) and pyridine (Fig. 1c), on the luminescent and gelation processes (Fig. 2). The study of new gold(i) structures is an area of special interest in supramolecular chemistry because of their potential anticancer activity and photophysical applications. 1-3 In this work, we present a series of new dialkynyl, carbene and dicarbene complexes () derived from hydroxycoumarin and imidazolium precursors. These compounds have been characterized by 1 H MR, IR and mass spectrometry. Their biological properties and those of their corresponding free ligands have been studied by testing their capability to inhibit TrxR and evaluating their IC 50 and antiproliferative effects in tumor cell lines. For the compounds and free ligands of the dialkynyl series, UV and luminescence studies have been carried out. The gold(i) compounds for the dialkynyl series (01-03), carbene series (04-09) and dicarbene series (10-12). Acknowledgements: Authors would like to thank the CST Action CM1005 for the opportunity to present this work. Financial support from MICI (project TEC C03-02) and the Generalitat de Catalunya (2009SGR158) is acknowledged. General structures of PTA derivatives Figure 2. Images of [AuC C-C5H4)(DAPTA)] by fluorescence optical microscopy Acknowledgements:Authors would like to thank funding provided by CST Action CM1005 Supramolecular Chemistry in water [1] Lima, J. C.; Rodríguez, L. Chem. Soc. Rev. 2011, 40, [2] R. Gavara, J. Llorca, J.C. Lima, L. Rodríguez, Chem. Commun. 2013, 49, [3] E. Aguiló, R. Gavara, J. C. Lima, J. Llorca, L. Rodríguez, submitted. [1] Lima, J. C.; Rodríguez, L., Anticancer Ag. Med. Chem. 2011, 11, 921. [2] Lima, J. C.; Rodríguez, L., Chem. Soc. Rev. 2011, 40, [3] Meyer, A.; Bagowski, C. P.; Kokoschka, M.; Stefanopoulou, M.; Alborzinia, H.; Can, S.; Vlecken, D. H.; Sheldrick, W. S.; Wölfl, S.; tt, I., Angew. Chem., Int. Ed. Engl. 2012, 51, PSTERS
44 PSTERS Poster 57 Synthesis of ew Chiral Tetraaza-Macrocycles and their Use as Ligands for Asymmetric Catalysis Poster 58 Cytotoxic Activity on HeLa Tumor Cell Lines of Cu(II) Complexes with Functionalized Quinolines Tommaso Pedrazzini, a* Marco Stanoppi, a Alessandro Caselli a Corrado Atzeri, a* Amelia Barilli, b Irene Bassanetti, a Luciano Marchiò a a Dipartimento di Chimica, Università degli Studi di Milano, Via Venezian 21, Milano, Italy, a Dipartimento di Chimica, Università degli Studi di Parma, Parco Area delle Scienze 17, Parma (PR), Italy; b Dipartimento di Scienze Biomediche, Biotecnologiche e Traslazionali, Via Volturno 39, Parma (PR), Italy; ur group has been focusing for years on the study of new chiral macrocyclic ligand. Their complexes with metal ions specially copper(i) are competent catalysts in various organic reactions. We obtained the best results, in terms of yield and enantioselectivity, on the asymmetric cyclopropanation. 1 We made several modifications on the structure of our ligands, to improve their effectiveness and their versatility. Here we reported an overview of these modifications and the preliminary results obtained using the new compounds in catalysis. In previous studies it was shown how copper complexes with pirazole-pyridine, donor ligands 1 or with 8- hydroxyquinoline derivatives 2 could induce cellular death in human tumor cell lines, by means of intracellular copper overload. This was due to the ability of the ligands to act as ionophores for copper-demanding tumor cells, which accumulated harmful quantities of metal ions inside the cell. As a continuation of these studies, we wished to investigate how the functionalization of the 8-hydroxyquinoline moieties with an aromatic side arm, with potential coordinating ability, could affect the anticancer activity of their Cu(II) complexes. The different substituents were chosen in order to modulate the overall ligand lipophilicity. A panel of 16 functionalized 8-hydroxyquinolinic ligands (L1-L16) were synthesized and tested for anticancer activity on human HeLa tumor cell line (cervical carcinoma). The ligands were tested alone and in presence of equimolar quantities of CuCl 2. A correlation was searched for between the exhibited cytotoxicities and structural features of the ligands. Some of the synthesized Cu(II) complexes were analyzed by means of single crystal XRD to evaluate the coordinating ability of the peripheral aromatic functionalization. Scheme 1 These compounds could be obtained in moderate to good yields (20-70%) following a simple synthetic path (scheme 1), based on the use of commercially available and enantiomerically pure reagents. We fully characterized the ligands including elemental analysis, MS, 1 H- and 13 C-MR. The nosyl protected ligands could easily be deprotected using the Fukuyama conditions 2 to obtain a not-protected dianionic class of macrocycles. We started testing the final compounds as ligands in copper(i) catalysts for asymmetric cyclopropanation with excellent results: in all cases we observed a complete conversion of EDA and, depending on the used ligand, we obtained cyclopropanes with stereoselectivities and e.e. up to 99% [1] Castano, B.; Guidone, S.; Gallo, E.; Ragaini, F.; Casati,.; Macchi, P.; Sisti, M.; Caselli, A. Dalton Trans. 2012, [2] Fukuyama, T.; Jow, C-K.; Cheung, M.; Tetrahedron Lett., 1995, 36, [1] Marchiò L. et al., J.Am. Chem. Soc. 2011, 133, [2] Marchiò L. et al., J. Med. Chem. 2012, 55,
45 Poster 59 Catalytic Studies With Model Complexes Mimicking the Hydrogenase Enzymes: Focus on Aromatic Dithiolate Ligand Complexes Poster 60 A Family of Dibenzobarrelene-Based Iridium Hydrides: Structural Peculiarities and the Interaction with Bases and Solvents Sandeep Kaur-Ghumaan* Department of Chemistry, University of Delhi, Delhi , India, Gleb Silantyev, a * leg A. Filippov, a Dmitri Gelman, b atalia V. Belkova, a Klaus Weisz, c Lina M. Epstein, a Elena S. Shubina c a A. esmeyanov Institute of rganoelement Compounds, Russian Academy of Sciences, Vavilov Street 28, Moscow, Russia; b Depletion of fossil fuels in the future is a serious concern. In this regard, hydrogen is being developed as an alternative energy source. Hence, special attention has been paid in recent years to molecular models of the hydrogenase (H 2ase) enzymes due to their remarkable efficiency in H 2 production and activation. Three types of H 2ases are known: the Fe-S cluster containing [FeFe] and [ife]- H 2ases and the Fe-S cluster-free [Fe]-H 2ase. 1-5 The [FeFe] and [ife] H 2ases participate in hydrogen production and/or oxidation while the [Fe] H 2ase engages mainly in hydrogen activation. The hydrogen evolution and activation has been studied by synthesizing and developing a large number of organometallic complexes. 6-7 But only a few of the complexes are capable of acting as catalysts for proton reduction or dihydrogen oxidation. Hence, the catalytic activities and properties of all the reported aromatic dithiolate (e.g. 1, 2-benzenedithiolate (bdt)) metal complexes will be summarized and reported. Examples of such complexes will include dinuclear organometallic complexes, [Fe 2( -bdt)(c) 5L] and [Fe 2( -bdt)(c) 4L 2] where L = Monodentate phosphines (). S S S S C L + C L Fe Fe Fe Fe C C L C C C C C Department of rganic Chemistry, the Hebrew University of Jerusalem, Philadelphia Bld., Givat Ram, Jerusalem, Israel; c Institut für Biochemie, Ernst Moritz Arndt Universität Greifswald, Felix-Hausdorff Straße 4, Greifswald, Germany; In the last decade cooperative ligands participated actively in reversible structural transformations of catalytic species over the course of a catalytic cycle, have been increasingly used to develop novel efficient catalysts in (de)hydrogenation processes. 1,2 Recently, the new class of polyfunctional dibenzobarrelene-based complexes exhibiting high catalytic activity in alcohol dehydrogenation and hydrofomrylation processes, was reported by Gelman et al. 3 In this contribution we present the recent results of the combined spectral (IR, MR) and theoretical investigation of a family of PC(sp 3 )P pincer iridium hydrides. The structural deversity of complexes 1 and 2 () was demonstrated on the base of both DFT calculations and experimental data. It was established that their structures had distorted pyramid geometry and differed by the mutual arrangement of ligands in the metal coordination sphere and by conformation of functional groups. The presence of triethylamine leads to the rupture of weak intramolecular interactions in 1 and the stabilization of 5-coordinated complexes by bases and solvents, e.g. DMS, pyridine, acetonitrile, results in the formation of novel structures. The structural peculiarities of 6-coordinated complexes 3 and 4 will be discussed as well. L = PPh 2 H, PPh 2 Me, PPh 3 [1] Vignais, P. M.; Billoun, B.; Meyer, J. FEMS Microbiol. Rev. 2001, 25, 455. [2] Shima, S.; Thauer, R. K. Chem. Rec. 2007, 7, 37. [3] Volbeda, A.; Charon, M. H.; Piras, C.; Hatchikian, E. C.; Frey, M.; Fontecilla-Camps, J. C. ature 1995, 373, 580. [4] Peters, J. W.; Lanzilotta, W.; Lemon, B. J.; Seefeldt, L. C. Science 1998, 282, [5] Shima, S.; Pilak,.; Vogt, S.; Schick, M.; Stagni, M. S.; Meyer-Klaucke, W.; Warkentin, E.; Thauer, R. K.; Ermler,U. Science 2008, 321, 572. [6] Kaur-Ghumaan, S. ; Schwartz, L.; Lomoth, R.; Stein, M.; tt, S. Angew. Chem. Int. Ed. 2010, 49, [7] Tard, C.; Pickett, C. J. Chem. Rev. 2009, 109, Acknowledgements: This work was financially supported by the Russian Foundation for Basic Research (projects o and ). [1] Gunanathan, C.; Shimon, L. J. W.; Milstein, D. J. Am. Chem. Soc. 2009, 131, [2] Käß, M.; Friedrich, A.; Drees, M.; Schneider, S. Angew. Chem. Int. Ed. 2009, 48, 905. [3] Azerraf, C.; Shpruhman, A.; Gelman, D. Chem. Commun. 2009, 466. PSTERS
46 PSTERS Poster 61 Rerversible rthometalation as ew Mode for Metal-Ligand Bifunctional Catalysis Poster 62 ickel-complexes Bearing Redox on-innocent Ligands Linda Jongbloed,* Jarl Ivar van der Vlugt Vincent Vreeken,* Jarl Ivar van der Vlugt Supramolecular & Homogeneous Catalysis Group, van t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The etherlands Homogeneous and Supramolecular Catalysis, van t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, the etherlands The active sites of enzymes often rely on the reactivity of neighboring ligand scaffolds and second coordination sphere interactions. With this cooperativity of the ligands, ature was able to employ earth-abundant first row transition metals, which incline to undergo one-electron processes, for controlled multi-electron reactions. 1 Recently the use of metal-ligand bifunctional ligands has been recognized as promising tool for the activation of substrates. 2-4 ur group is interested in the targeted design of new non-innocent ligand architectures for cooperative bond activation reactions and catalytic processes. 5 Many of the metal-ligand bifunctional catalyst that show excellent results in substrate activation, are based on the robust, reactive and easily modified pincer ligands. For a long time, the pincer chemistry was dominated by E-C-E (E = P, S) ligands with a orthometalated central ring. It is surprising to see that the M-C bond never has been explored as cooperative motif, since C-H activation methodologies provide powerful and efficient pathways for hydrocarbon functionalization. 6 This poster shows the synthesis of new proton-responsive orthometalated complexes with a phenyl group in the terminal position to avoid steric restrictions (). The reactivity of the M-C bond and application in catalytic reactions are explored. Redox non-innocence allows ligands to become part of the catalytic cycle. These ligands have drawn attention the past decade because they may offer ways to induce new reactivity to metal complexes. Ligands in these complexes are no longer spectators but actors, the key idea behind cooperative catalysis. 1,2 ne way redox non-innocent ligands can be employed is to let them function as an electron reservoir. First-row transition metals often promote one electron redox changes while essential steps in catalysis, such as oxidative addition and reductive elimination are two electron processes. 3 Additionally, redox non-innocent ligands can be employed to generate ligand-based radicals. In this way, interesting ligand-based reactivity can be induced. 4 ickel complexes containing a monoanionic PP-pincer ligand are known to form ligand-based aminyl radicals upon oxidation (figure 1). 5 We are interested in studying the reactivity of these complexes. This relates to their potential to be used for amination reactions and to support relevant intermediates in 2 reduction pathways. We will present the latest developments in our research on synthesis, characterization and reactivity of redox noninnocent ligands and their corresponding metal complexes. [1] van der Vlugt, J. I., Eur. J. Inorg. Chem. 2012, 3, 363. [2] van der Vlugt, J. I.; Reek, J. H. Angew. Chem. Int. Ed. 2009, 48, [3] Gunanathan, C.; Milstein, D. Acc. Chem. Res. 2011, 44, 588. [4] Kashiwame, Y.; Kuwata S.; Ikariya, T. Chem. Eur. J. 2010, 16, 766. [5] a) van der Vlugt, J. I.; Pidko, E. A.; Vogt, D.; Lutz, M.; Spek, A. L. Inorg. Chem. 2009, 48, 7513; b) de Boer, S. Y.; Gloaguen, Y.; Reek, J. H.; Lutz, M.; van der Vlugt, J. I. Dalton Trans. 2012, 41, [6] a) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, b) Engle, K. M.; Mei, T.; Wasa, M.; Yu, J. Acc. Chem. Res. 2012, 45, 788. [1] Lyaskovskyy, V.; de Bruin, B. ACS Catal. 2012, 2, 270. [2] van der Vlugt, J. I. Eur. J. Inorg. Chem. 2012, 363. [3] Chirik, P. J.; Wieghardt, K. Science 2010, 327, 794. [4] Dzik, W. I.; van der Vlugt, J. I.; Reek, J. H.; de Bruin, B. Angew. Chem. Int. Ed. 2011, 50, [5] Adhikiri, D.; Mossin, S.; Basuli, F.; Huffman, J. C.; Szilagyi, R. K.; Meyer, K.; Mindiola, D. J. Inorg. Chem. 2008, 47,
47 Poster 63 ew Effective Ligands for Cu-Catalysed Aryl Ether Formation in Air Poster 64 RuCl 3 Catalyzed Transfer Hydrogenation of atural Polyenes Mixture to Monoenes Carlo Sambiagio, a * Patrick C. McGowan, a Steven P. Marsden, a A. John Blacker, a Rachel Munday b Sébastien C. P. Perdriau,* Sjoerd Harder, Hero J. Heeres, Johannes G. de Vries a School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK, b AstraZeneca Ltd., Pharmaceutical Development, Hulley Road, Macclesfield, SK10 2A, UK, University of Groningen, Stratingh Institute of Chemistry & Dept. of Chemical Engineering, ijenborgh 4, 9747 AG Groningen, The etherlands, Aryl ethers are important motifs in medicinal chemistry, and the use of Cu-catalysed couplings (Ullmann reactions) for their synthesis is nowadays a common procedure. 1 Typically these reactions require simple neutral or anionic ligands and are performed under inert atmosphere. However, the role of the ligand in these reactions is not totally understood, and only a few structure-activity relationship studies on families of ligands have been reported. 2 Herein, we report investigations on a new class of ligands for Ullmann ether synthesis under mild conditions. Compared with other common ligands (L1-L10), ligand L11 led to higher yields in a model reaction in several condition tested (Scheme 1). In particular, the reaction could be performed in air without any decrease in yield. ptimisation of the reaction, substrate screening and mechanistic investigations aiming to understanding the interactions ligand / metal centre are ongoing in our laboratories. Cashew ut Shell Liquid (CSL) a waste from agriculture is rich in Anacardic Acid and Cardol. Technical CSL is obtained by decarboxylation of CSL which leads to a mixture mainly composed of Cardanol and Cardol (> 95%). These unsaturated components can be separated by different methods using liquid-liquid extraction or vacuum distillation. These phenolic olefins are mixtures of a triene, a diene, a monoene and a saturated compound. 1 These mixtures of polyenes can be converted into a single monoene by catalytic hydrogenation or transfer hydrogenation using, formic acid or an alcohol as hydrogen source. The reactivity of a number of different catalysts was compared. Very high selectivity was obtained by transfer hydrogenation with RuCl 3 using isopropanol as reducing agent. Surprisingly, it was found that RuCl 3 is not converted to nanoparticles as expected. Rather, the substrate forms a ligand to the metal. Complexes with one, two or three substrate molecules attached to ruthenium were found. It was also shown that interaction between the ruthenium metal and the aryl moiety is important for activity. As a result, this procedure could also be applied to polyunsaturated fatty acid derivatives, but only introducing a phenyl function. This is the first instance of a catalyst that is activated by the presence of an aromatic ring in the substrate. 2 Scheme 1 [1] Tyman, J., Tychopoulos, V., Chan, P., J. Chromatography A 1984, 303, 137. [2] Perdriau, S., Harder, S., Heeres, H. J., de Vries, J. G. ChemSusChem 2012, 12, Scheme 1 [1] Evano, G.; Blanchard,. and Tuomi, M. Chem. Rev. 2008, 108, [2] uali, A.; Spindler, J. F.; Jutand, A. and Taillefer, M. Adv. Synth. Catal. 2007, 349, PSTERS
48 PSTERS Poster 65 Methods of Preparing a Chiral Precursor of Mivacurium Chloride Poster 66 n the Mechanism of Asymmetric Transfer Hydrogenation of Imines Beáta Vilhanová, a * Václav Matoušek, a Jiří Václavík, a Jan Pecháček, a Petr Šot, a Marek Kuzma, b Petr Kačer a Jiří Václavík, a * Marek Kuzma, b Petr Šot, a Jan Pecháček, a Beáta Vilhanová, a Petr Kačer a a Department of rganic Technology, Institute of Chemical Technology, Technická 5, Prague 6, Czech Republic; b Laboratory of Molecular Structure Characterization, Institute of Microbiology, v.v.i., Academy of Sciences of the Czech Republic, Vídeňská 1083, Prague 4, Czech Republic; a Department of rganic Technology, Institute of Chemical Technology, Technická 5, Prague 6, Czech Republic, b Laboratory of Molecular Structure Characterization, Institute of Microbiology, v.v.i., Academy of Sciences of the Czech Republic, Vídeňská 1083, Prague 4, Czech Republic. Mivacurium chloride () belongs to skeletal muscle relaxants with a short duration of action, which are frequently used in surgery under anaesthesia. Like many other relaxants (and drugs in general), Mivacurium is a chiral molecule and must be administered to patients in the form of a single enantiomer. The optically pure fragment of the drug, (R)-5ʹmethoxylaudanosine, is typically produced by separation of racemic mixture. In this work, we present the synthesis of a precursor of Mivacurium chloride (and other structurally similar relaxants, e.g. Gantacurium), which was prepared via two different routes. The first way reproduces the procedure established in the industry because no detailed information about the reaction conditions was available hitherto. The second synthesis is based on the asymmetric transfer hydrogenation of a dihydroisoquinoline followed by -methylation. Both methods were feasible, but the asymmetric pathway seemed to be more economical and ecological than the industrial route. Structure of Mivacurium chloride (the chiral fragment is shown in blue colour). Asymmetric transfer hydrogenation (ATH) of prochiral imines is nowadays a fairly well-documented method for the preparation of optically enriched amines. 1 The reaction is catalyzed by chiral half-sandwich ruthenium complexes [RuCl(η 6 - arene)(-arylsulfonyl-dpe)] (DPE = 1,2-diphenylethylene-1,2-diamine). The azeotropic mixture of formic acid and triethylamine serves as the hydrogen donor. The mechanism of ATH of imines (and ketones) has been extensively studied since the discovery of the catalytic system. Although the number of publications on this topic is considerably high, one may be easily confused due to a high degree of fragmentation of the C 2 H Ru findings presented therein. Ts H Therefore, the aim of this work H Ph Ph is to give a concise but coherent Ru-hydride description of the contemporary H Ru mechanism (). Several Ts TS2 contributions of our group on H H Ph Ph this topic are included, such as calculated geometries of the transition states, 2 influence of the base on the reaction performance, 3 and the formation of the key ruthenium hydride species. H Ru Ts H H Ph Ph ATH H + H + Ru Ts Cl Ru Ts H H H Ph H Ph Ph Ph Ru-solvate Ru-Cl HC H Ru TS1 Ts H Ru-formate H Ph Ph. Schematic representation of the mechanism of imine ATH. Acknowledgements: This work has been financially supported by the Grant Agency of the Czech Republic (Grant GACR P106/12/1276), and by grant for long-term conceptual development of Institute of Microbiology RV: Acknowledgements: This work has been financially supported by the Grant Agency of the Czech Republic (Grant GACR P106/12/1276), and by grant for long-term conceptual development of Institute of Microbiology RV: [1] Václavík, J.; Kačer, P.; Kuzma, M.; Červený, L. Molecules 2011, 16, [2] Václavík, J.; Kuzma, M.; Přech, J.; Kačer, P. rganometallics 2011, 30, [3] Kuzma, M.; Václavík, J.; ovák, P.; Přech, J.; Januščák, J.; Červený, J.; Pecháček, J.; Šot, P.; Vilhanová, B.; Matoušek, V.; Goncharova, I. I.; Urbanová, M.; Kačer, P. Dalton Trans. 2013, 42, 5174.
49 Poster 67 ovel (arene)ruthenium(ii) Complexes with halogen-substituted Scorpionates: Synthesis and Structural, Electrochemical and Catalytic Studies Poster 68 ew Cationic -Heterocyclic Carbene Gold(I/III) Pyridine Complexes: Synthesis, Characterization and Catalytic Activity Serena rbisaglia, a * Corrado Di icola, b Francesca Condello, a Jessica Palmucci, a Riccardo Pettinari, b Fabio Marchetti, a Claudio Pettinari, b Luísa M.D.R.S. Martins, c,d Elisabete C.B.A. Alegria, c,d M. Fátima C. Guedes da Silva, d,e Bruno G.M. Rocha, d Armando J.L. Pombeiro, d Brian W. Skelton, f,g Allan H. White f a School of Science and Technology and b School of Pharmacy, Via S. Agostino 1, Camerino (MC), Italy; c Chemical Engeneering Departamental Area, ISEL, R. Conselheiro Emídio avarro, Lisbon, Portugal; d Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Technical University of Lisboa, Av. Rovisco Pais, Lisbon, Portugal; ev Universidade Lusófona de Humanidades e Tecnologias, ULHT Lisbon, Campo Grande 376, Lisbon, Portugal; f School of Chemistry and Biochemistry M310 and g Centre for Microscopy, Characterisation and Analysis, The University of Western Australia, Crawley, WA 6009, Australia; Since their discovery in 1966, 1 poly(pyrazolyl)borates (Bp x and Tp x ), often indicated as scorpionates, have been extensively employed as anionic -donor ligands in a wide variety of metal complexes, 2 as the steric and electronic properties of these ligands are easily modified by changing either the number of pyrazole rings or by substituents thereon or at the boron/carbon center. In recent works, we investigated the interaction of η 6 -arene Ru(II) with (pyrazol-1-yl)borates 3 and (pyrazol-1-yl)alkanes, 4 their coordination chemistry and their catalytic behaviour. Here we report some recent results obtained with bis- and tris-pyrazolylborate ligands bearing Br and i Pr substituents in the pyrazole rings (Fig. 1) and some η 6 - arene ruthenium fragments (arene = benzene, para-cymene or hexamethylbenzene), together with the spectroscopic and structural characterization of the organometallic complexes. The comparison of the electron-donor character of Bp - and Tp - ligands has been supported by electrochemical studies. Furthermore preliminary catalytic results on diastereoselective nitroaldol reaction of benzaldehyde and nitroethane (Henry Reaction) will be reported. Serena rbisaglia, a,b * Béatrice Jacques, b Pierre Braunstein, b Damien Hueber, c Patrick Pale, c Aurélien Blanc, c Pierre de Frémont b a School of Science and Technology, Via S. Agostino 1, Camerino (MC), Italy; b Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, Strasbourg, France; c Laboratoire de Synthèse, Réactivité rganique et Catalyse, Institut de Chimie (UMR 7177 CRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, Strasbourg, France; Since the isolation of the first free stable -Heterocyclic Carbene (HC) by Arduengo in 1991, 1 organogold chemistry and gold catalysis have taken full advantage from the easy use of this class of ligand. 2 Indeed, the strong electron donor ability and the easy tuning of steric properties of HCs stabilize gold centers in various oxidation states 3 and many complexes initially thought to be elusive could be isolated and structurally characterized. 4 Therein, here we describe the synthesis and characterization of a new series of stable, cationic HC gold(i/iii) pyridine complexes, as well as their stability and catalytic activity in five well established gold-mediated organic transformations. [1] Trofimenko, S. J. Am. Chem. Soc., 1966, 88, [2] (a) Trofimenko, S. Scorpionates - The Coordination Chemistry of Polypyrazolylborate Ligands; Imperial College Press: London, (b) Pettinari, C. Scorpionates II: Chelating borate ligands; Imperial College Press: London, [3] Pettinari, C.; Marchetti, F.; Cerquetella, A.; Pettinari, R.; Monari, M.; Mac Leod, T. C.; Martins, L. M. D. R. S.; Pombeiro, A. J. L. rganometallics, 2011, 30, [4] Marchetti, F.; Pettinari, C.; Pettinari, R.; Cerquetella, A.; Di icola, C.; Macchioni, A.; Zuccaccia, D.; Monari, M.; Piccinelli, F. Inorg. Chem. 2008, 47, [1] Arduengo, A. J. III; Harlow, R. L.; Kline, M. J. Am. Chem. Soc., 1991, 113, 361. [2] (a) Marion,.; olan, S. P. Chem. Soc. Rev., 2008, 37, (b) Hashmi, A. S. K. Angew. Chem. Int. Ed., 2010, 49, (c) olan, S. P. Acc. Chem. Res., 2011, 44, 91. (d) Rudolph, M.; Hashmi, S. K. Chem. Soc. Rev., 2012, 41, [3] Lin, J. C. Y.; Huang, R. T. W.; Lee, C. S.; Bhattacharrya, A.; Hwang, W. S.; Lin, I. J. B. Chem. Rev., 2009, 109, [4] (a) de Frémont, P.; Stevens, E. D.; Fructos, M. R.; Díaz-Requejo, M. M.; Pérez, P. J.; olan, S. P. Chem. Commun., 2006, (b) de Frémont, P.; Marion,.; olan, S. P. J. rganomet. Chem., 2009, 694, 551. (c) Ramόn, R. S.; Gaillard, S.; Poater, A.; Cavallo, L.; Slawin, A. M. Z.; olan, S. P. Chem. Eur. J., 2011, 17, (d) Jacques, B.; Kirsch, J.; de Frémont, P.; Braunstein, P. rganometallics, 2012, 31, PSTERS
50 PSTERS Poster 69 Sensitization of Monolayer Transparent Ti 2 Thin Films with Metal-Porphyrin Dyes for DSSC Applications. Equilibrium and Kinetic Aspects Poster 70 Enantioselective Transfer Hydrogenation of Aryl-Ketones and Stereochemistry of the Metal Centre by MR and CD Spectroscopy Marco Zannotti,* Chiara Anna D Amato, Rita Giovannetti Isabella Rimoldi, Giorgio Facchetti, Edoardo Cesarotti, Michela Pellizzoni, Marco Fusè,* Daniele Zerla School of Environmental Sciences, Via S. Agostino 1, Camerino (MC), Italy. For the best manufacture of dye-sensitized solar cell (DSSC) systems (), optimum objectives are represented from very rapid and complete adsorption of single layer of dye on the semiconductor surface. 1,2 Cu(II) and Zn(II) complexes of Coproporphyrin-I or CPI (Figure 2), has been synthesized in our laboratory and tested as sensitizers in DSSC devices. 3,4 A systematic study of kinetic and equilibrium for the adsorption of metal-cpi-dyes onto Ti 2 monolayer surfaces, have permit to establish the best experimental conditions for the adsorption of these dyes and have demonstrated that the metal-cpi-dyes, according to the Langmuir model and with pseudo first-order kinetics, are adsorbed effectively in the support of Ti 2 monolayer without chemical changes. The suppression of the dyes aggregation have permitted the optimization of selective adsorption of one layer of dyes molecules to stoichiometric ratios improving performances in DSSC indicating therefore a powerful experimental strategy, that can be enlarged to other dyes. Università degli Studi di Milano, Dipartimento di Scienze Farmaceutiche, sezione di Chimica Generale e rganica, Via Golgi 19, Milano, Italy Ruthenium complexes are the most useful catalyst for AH and AHT of polarized bonds. 1,2 Among the multitude of ruthenium complexes, those gathering a diamine chiral ligand and a diphosphine are particularly efficient. ptically pure 8- amino-5,6,7,8-tetrahydroquinoline (hereafter defined Campy) showed to be a versatile source of chirality, particularly in AHT, 3 with chiral and achiral diphosphine. The great enantioselective efficiency seems to be related to the formation of only one of the possible chiral catalytic species. In the monohydride complex (inactive in AHT without the presence of CH(CH 3) 3- ) the formation of the chiral metal centre is stereoselctive and likely proceeds with retention of configuration. We will discuss in detail the relation among CD of LF transitions, MR ESY and CSY correlations and the stereochemistry of AHT reduction of prochiral ketons. H H M H. DSSC Process H Figure 2. Molecular structures of Coproporphyrin-I sensitizers, CPI = M is no metal, CPIZn =M is Zn(II), CPICu = M is Cu(II). [1] Graetzel, M. ature 2001, 414, 338. [2] Hagfeldt, A.; Boschloo, G. L.; Sun, Kloo, L.; Pettersson, H. Chem. Rev. 2010, 110, [3] Giovannetti, R.; Alibabaei, L.; Petetta, L.; J. Photochem. Photobiol. A: Chemistry, 2010, 211, 108. [4] Alibabaei, L.; Wang, M.; Giovannetti, R.; Teuscher, J.; Moser, J-E.; Compte, P.; Pucciarelli, F.; Zakeeruddin, S.M.; Graetzel, M. Energy Env. Sci. 2010, 3, 956. [1] oyori, R.; hkuma, T. Angew. Chem. Int. Ed. 2001, 40, 40. [2] Clapham, S. E.; Hadzovic, A.; Morris, R. H. Coord. Chem.Rev. 2004, 248, [3] Rimoldi, I.; Facchetti, G.; Cesarotti, E.; Pellizzoni, M.; Fuse, M.; Zerla, Daniele Curr.rg. Chem. 2012, 16, 2982.
51 Poster 71 Zn Salophen Complexes and Macro Cycles as Hosts in Molecular Recognition of Anions Ferran Sabaté, a * Ilaria Giannicchi, b Antonella Dalla Cort, b Laura Rodríguez a Poster 72 Synthesis of ovel Salen Ruthenium(II) Complexes Fenna van de Watering,* Joost Reek University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The etherlands, a Departament de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1 11, Barcelona, Spain; b Dipartimento di Chimica e IMC-CR, Università La Sapienza, P.zzle A. Moro 5, Rome, Italy; * Sensing of anions is an increasing research area in chemistry and even more in biochemistry. Biologically relevant species usually bear negative charges. ne strategy to detect this species is to capture them through a coordinative or electrostatic bond that brings the anion near an adequate signaling unit whose fluorescent properties are affected by the coordination. Salophen metal complexes, which bear a vacant coordination position, are very appealing candidates in applications related with anion sensing. 1 In this work, we present the use of different Zn-salophen derivatives that differ on the electronic character of one substituent (a). We analyze how this could affect on the molecular recognition processes of anions in solution. Moreover, we present the synthesis of a macro cycle that can host larger anions (Figure 1b). 2 Salens are distinct ligands that have been applied extensively in asymmetric catatlysis. 1 Their simplicity of preparation and easy accessible dive. 2 ext to the common and widely used trans geometry for catalytic systems, also the less common cis-α and cis-β configurations (see ) exist. It has been shown that the latter configuration gives rise to different and unique asymmetric catalytic properties. 3,4 Recently, also binuclear species are shown to enhance catalytical performance5. but not much research has been performed in a combination of these two with ruthenium as a metal. 4,6 9 Therefore, the two chiral Schiff bases consisting of a bismethylphenyl-(l1) or bisnapthyl backbone (L2), that are known to favour a non planar coordination geometry, have been prepared. The geometries of these ligands coordinated to ruthenium were investigated, as well as their (cooperative multimetallic) catalytic properties. Three different geometries of metallosalens in space (a); Two ligands that favour a non planar coordination geometry (b). Acknowledgements: Support and sponsorship provided by CST Action CM1005 is acknowledged. [1] Cano, M.; Rodríguez, L.; Lima, J.C.; Pina, F.; Dalla Cort, A.; Pasquini, C.; Schiaffino, L. Inorg. Chem. 2009, 48, [2] Sheu, J-F.; Wei, H-H. J. Chinese Chem. Soc. 1989, 36, 539. [1] Matsunaga, S.; Shibasaki, M. Synthesis 2013, 45, [2] Katsuki, T. Synlett 2003, 3, [3] Katsuki, T. Chem. Soc. Rev. 2004, 33, [4] Xu, Z.-J.; Fang, R.; Zhao, C.; Huang, J.-S.; Li, G.-Y.; Zhu,.; Che, C.-M. J. Am. Chem. Soc. 2009, 131, [5] Haak, R. M.; Wezenberg, S. J.; Kleij, A. W. Chem. Commun. 2010, 46, [6] Sauve, A. A.; Groves, J. T. J. Am. Chem. Soc. 2002, 7, [7] Munslow, I. J.; Gillespie, K. M.; Deeth, R. J.; Scott, P. Chem. Commun. 2001, 1, [8] Thornback, J. R.; Wilkinson, G. Dalton Trans. 1978, [9] g, H.-Y.; Lam,.-M.; Yang, M.; Yi, X.-Y.; Williams, I. D.; Leung, W.-H. Inorg. Chim. Acta 2013, 394, PSTERS
52 PSTERS Poster 73 Cooperative Ligand Effects in Hydride Transfer Catalysis Poster 74 Closed-shell and pen-shell Group 9 Transition Metal itrido Complexes Zhou Tang,* Jarl Ivar van der Vlugt, Joost. H. Reek, Bas de Bruin Markus G. Scheibel, a Edward J. Reijerse, b Bas de Bruin, c Sven Schneider a * Supramolecular & Homogeneous Catalysis, Van t Hoff Institute for Molecular Science, University of Amsterdam, The etherlands, a Georg-August University, Tammannstraße 4, Göttingen, Germany; b Max-Planck Institute for Energy Conversion, Stiftstr , Mühlheim a. d. Ruhr, Germany; c van t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, XH 1098 Ansterdanm the etherlands; Transfer Hydrogenation (TH) is an important and well-studied process in chemistry, which involves stepwise dehydrogenation (hydrogen donor) and hydrogenation (hydrogen acceptor) of substrates. Conceptually relevant reactions in this field include dehydrogenation, dehydrogenative coupling, and hydrogen auto-transfer (borrowing hydrogenation methodology), which are all hot topics in current catalysis research. 1 Transition metal (TM) complexes featuring ligandcooperative effect to facilitate the hydrogen transfer process have been intensively studied and well developed. 2 Ligands in such systems generally serve as a proton-relay site, while the hydride is typically received and delivered by the metal center. In nature, however, reduction of unsaturated bonds often involves organic hydride donors, with ADH and Flavins among the most well-known examples. Rare cases have been reported in these TH-related catalysis with the ligand of the TM complexes promoting a hydride transfer. 3 In this poster we present a new concept, in which a new cooperative ligand system is developed that acts an hydride donor/acceptor in transfer-hydrogenation type catalysis. This system is based on the picolyl-amine type scaffold, and allows for a variety of catalytic hydride transfer reactions such as TH and hydrogen autotransfer coupling reactions, thus showing the potential of this new system. n the basis of DFT calculations a new ligand-assisted hydride-transfer mechanism is revealed for this reaction, involving a low-barrier amine to imine interconversion as the key-step of the overall catalytic process (). TM Complexes with a new family of P ligands have been developed (Figure 2). The ligands can potentially function in the catalysis as a dual shuttle for both protons and hydrides. Electron rich transition metal nitrido complexes are under great current interest in the context of dinitrogen fixation and catalytic nitrogen group transfer reactions. 1 pen-shell nitrido complexes were postulated as intermediates in nitride coupling, but examples remain scarce. 2,3 Based on electronically and coordinatively unsaturated iridium and rhodium PP pincer platforms, 4 we were able to characterize high-valent iridium(v) and iridium/rhodium(iv) nitrido complexes. 5 The electronic structure and reactivity of this class of compounds is discussed, 6 particularly the highly selective nitride coupling reaction of the open shell nitrides which is attributed to a radical coupling reaction due to pronounced nitridyl character. [1] Berry, J. A. Comm. Inorg. Chem. 2009, 30, 28. [2] a) Kane-Maguire, L. A. P.; Sheridan, P. S.; Basolo, F.; Pearson, R. G. J. Am. Chem. Soc. 1970, 92, b) Buhr, J. D.; Taube, H. Inorg. Chem. 1979, 18, [3] Allaga-Alcade,.; DeBeer Gorge, S.; Mienert, B.; Bill, E.; Wieghardt, K.; eese, F. Angew. Chem. Int. Ed. 2005, 44, [4] Meiners, J.; Scheibel, M. G.; Lemée-Cailleau, M.-H.; Mason, S. A.; Boeddinghaus, B.; Fässler, T. F.; Herdtweck, E.; Khusniyarov, M. M.; Schneider, S. Angew. Chem. Int. Ed. 2011, 50, [5] Scheibel, M. G.; Askevold, B.; Heinemann, F. W.; Reijerse, E. J.; de Bruin, B.; Schneider, S. ature Chem. 2012, 4, 552. [6] Scheibel, M. G.; Klopsch, I.; Stollberg, P.; Wolf, H.; Stalke, D.; Schneider, S. Eur. J. Inorg. Chem. 2013, DI: /ejic Figure 2 [1] Williams, M. J. Adv. Synth. Catal. 2007, 349, 1555; Crabtree, R. H. Chem. Rev. 2010, 110, 681. [2] Milstein, D. Acc. Chem. Res. 2011, 44, 588; van der Vlugt, J. I., Reek, J. H., Angew. Chem. Int. Ed. 2009, 48, [3] Colbran, S. B. Chem.Soc.Rev. 2013, 42, 5439.
53 Poster 75 A ew Class of anoscaffolds based on Ion Tagged Ti(IV) Amine Triphenolate Complexes R. Di Lorenzo,* A. Mroczek, E. Amadio, C. Miceli, C. Zonta, G. Licini Department of Chemical Sciences, Via Marzolo, 1, 35131, University of Padova, Italy, Triphenolamines are highly modular ligands that are able to effectively coordinate to a wide variety of transition metal ions, leading to the formation of a large family of complexes. 1 As referred to Ti(IV) complexes, the nature of the substituent in para position to the phenol groups is important to determine the binding mode and the stability of the corresponding complexes in solution. In particular, when the substituent is a phenyl group, the complexation reaction leads to the formation of exceptionally stable S 6-symmetric heterochiral μ-oxo dinuclear complexes (scheme 1). 2 Poster 76 ldies but Goodies: Back to Ruthenium(II) Complexes Sara Muzzioli, a * Stefano Stagni, a icola Sangiorgi, c Alessandra Sanson, c Massimo Cocchi b a Department of Industrial Chemistry Toso Montanari, Viale del Risorgimento 4, Bologna (B), Italy; b Istituto ISF-CR, Via P. Gobetti 101, Bologna (B), Italy; c Istituto ISTEC-CR, Via Granarolo, 64 I, Faenza (RA), Italy; Following our studies on tetrazolato-based Ru(II)-polypiridyl complexes, which showed remarkable photophysical properties and have also been reported as good emitters for Electrochemilumescent devices, 1 we have developed new Ru(II)-tetrazolate neutral system that might be used either as light absorber for DSSC(dye sensitizer solar cell) or as dopants for LED type devices (). Scheme 1 Here the synthesis of 1 based on a three-fold reductive amination as well as the highly effective three fold para formylation to obtain ligand 2 will be presented. The further functionalization of 2 via oxime bond formation allows the introduction of ion tagged and PEG moieties which can tune the solubility of the ligands 3 in polar/protic solvents. Moreover, their corresponding spatially ordered dinuclear complexes 4 can be employed to build up supramolecular systems and molecular scaffolds for further applications in catalysis and material sciences. Acknowledgments: We thank CST Action CM 1005 Supramolecular Chemistry in Water for financial support. [1] Stagni, S.; Palazzi, A.; Zacchini, S.; Ballarin, B.; Marcaccio, M.; Paolucci F.; Bruno C.; Monari M.; Carano M.; Bard, A.J. Inorg. Chem. 2006, 45, 695; Zanarini, S.; Bard, A.J.; Marcaccio, M.; Palazzi, A;. Paolucci, F.; Stagni, S. J. Phys. Chem. B, 2006, 110, 22551, Stagni, S.; rselli, E.; Palazzi, A.; De Cola, L.; Zacchini, S.; Femoni, C.; Marcaccio, M.; Paolucci, F.; Zanarini, S.; Inorg. Chem. 2007, 46, 9138, Stagni, S.; Palazzi, A.; Brulatti,P.; Salmi, M.; Muzzioli, S.; Zacchini, S.; Marcaccio, M.; Paolucci, F.; Eur. J. Inorg. Chem , 29, [1] Licini, G.; Mba, M.; Zonta, C. Dalton Trans. 2009, 27, [2] Bernardinelli, G.; Seidel, T. M.; Kundig, E. P.; Prins, L. J.; Kolarovic, A.; Mba, M.; Pontini, M.; Licini, G. Dalton Trans. 2007, PSTERS
54 PSTERS Poster 77 ew Synthetic Methods for rganometallic Ketonyl Derivatives of the Type [PtCl{ 1 - CH 2 C()R}(-)] Starting from the Zeise s Salt Michele Benedetti, a Chiara R. Girelli, a * Daniela Antonucci, a Sandra A. De Pascali, a Francesco P. Fanizzi a a Dipartimento di Scienze e Tecnologie Biologiche ed Ambientali, Università del Salento, Via Prov.le Lecce-Monteroni, Lecce, Italy, The reactivity of the Zeise s anion with bidentate dinitrogen ligands (-) has been the main subject of several studies on the Pt(II) coordination and organometallic chemistry. 1 The chemistry of Pt(II) organometallic ketonyl derivatives it is recognized to be important for many potential applications, 2 where the peculiar properties of ketonyl derivatives with transition metals seem of particular interest 3. For these reasons we exploit the possible extension of Zeise s anion reactivity, in basic media, to the general synthesis, of organometallic ketonyl derivatives of the type [PtCl{ 1 -CH 2C()R}(-)], even in the case of aliphatic diamines and sterically hindered diimine ligands. In these conditions we observed the first formation of methastable intermediate complexes of the type trans-[ptcl 2{ 1 -CH 2C()R}( 2 -C 2H 4)]. Further reaction with dinitrogen ligands (-) gives [PtCl{ 1 -CH 2C()R}(-)] complexes (). We were able to synthesize for the first time [PtCl{ 1 -CH 2C()R}(- )] complexes with sterically unhindered or hindered diamine and diimine nitrogen ligands, i.e. en (ethylenediamine), tmen (, -tetramethyl-ethylenediamine), Me 2phen (2,9-dimethyl-1,10-phenanthroline). In particular we could verify the usefulness of this new method for the synthesis, in high yields, of acetonyl derivatives, even in the case of complexes previously obtained by other synthetic pathways, as the complex [PtCl{ 1 -CH 2C()R}(phen)], phen = 1,10-phenantroline. 4 This new simple pathway results interesting from the synthetic point of view for the possibility to synthesize ketonyl complexes with several ketones and dinitrogen ligands not suitable for other methods. _ Cl Cl Cl H + H +RC()CH 2 Cl H 2 C C R - H 2 C C R Pt Pt Cl Pt Pt -H -C 2 H 4 Cl Cl Cl -Cl Cl Poster 78 Solventless VC chemisorption by silver metallocycles C. S. umarou,* a S. Tekarli, b V. esterov, b M. A. mary, b A. Burini, a R. Galassi a a School of Science and Technology, Chemistry Division, University of Camerino, Via S. Agostino 1, Camerino; b Department of Chemistry, University of orth Texas, Denton, TX 76203, USA; Prior work has focused on detection/sensing aspects of VCs, 1,2 this work proposes a method for their simultaneous filtration and removal through their strong chemisorption to a silver(i) metallocyclic trimer. A solid cyclotrimer can quantitatively remove entire molar integers of VCs (1-3 equivalents of VCs per mole of the nitrated trimer) from the vapor phase in a solventless green chemical process, which is unprecedented for this class of cyclic d 10 complexes. [1] Benedetti, M.; Fanizzi, F. P.; Maresca, L.; atile,g. Chem. Commun. 2006, 10, 1118; Benedetti, M.; Barone, C. R.; Antonucci, D.; Vecchio, V. M.; Ienco, A.; Maresca, L.; atile, G.; Fanizzi, F. P. Dalton Trans. 2012, 41, [2] Akiba, M.; Sasaki, Y. Inorg. Chem. Commun. 1998, 1, 61; Seebach, D. Angew. Chem. Int. Ed. 1988, 27, [3] Masamune, S.; Choy, W.; Petersen, J. S.; Sita, L. R. Angew. Chem. Int. Ed. 1985, 24, 1. [4] Barone, C. R.; de Pinto, S.; Maresca, L.; atile, G.; Pacifico, C. Inorg. Chim. Acta 2012, 383, 13. Illustration of quadrupole-dipole interactions involving the [Ag(μ-Pz-2CF3)]3 or [Ag(3,5-(2)2pz)]3 trimers and acetonitrile using M06/CEP-31G(d). MEP surfaces are plotted in two manners, either mapped on electron density surfaces (rainbow plots with the color scale shown; isodensity = ) or positive (blue) and negative (red) regions in space (range = ± 2.2 a. u.; isodensity = 0.02) [1] Yaghi,. M. et al. PAS 2008, 105, [2] Galassi, R.; Ricci, S.; Burini, A.; Macchioni, A.; Rocchigiani, L.; Marmottini, F.; Tekarli, S.; esterov, V.; mary, M. A. J. Am. Chem. Soc. 2013, submitted.
55 Poster 79 Highly Symmetric Dinuclear Ti(IV) anostructures Poster 80 A ew Synthetic Procedure for Multifunctionalized C 3 Triphenolamines E. Amadio,* a R. Di Lorenzo, b C. Miceli, a A. Mroczek, b C. Zonta, b G. Licini b * C. Miceli,* a,b E. Amadio, a,b R. Di Lorenzo, b C. Zonta, b G. Licini b a Istituto per la Tecnologia delle Membrane (ITM-CR) c/o Università di Padova, via Marzolo 1, 35100, Padova, Italy; b Dipartimento di Scienze Chimiche, Università di Padova, via Marzolo 1, Padova, Italy; a Istituto per la Tecnologia delle Membrane, (ITM-CR) c/o Dipartimento Scienze Chimiche, via Marzolo, 1, Padova, Italy; b Dipartimento di Scienze Chimiche, Università di Padova, via Marzolo 1, Padova, Italy; Mononuclear Ti(IV) complex 1 (R=R =H), obtained by reaction of Ti(iPr) 4 with amine triphenolate ligand bearing ortho-phenyl substituents, has been found to quantitatively and spontaneously reacts with water affording the corresponding heterochiral -oxo dinuclear complex 2 (). 1 This highly stable and spatially ordered μ-oxo dinuclear complex has twelve potential anchoring sites for the selective functionalization: six correspond to the meta positions of the peripheral phenyl moieties (R ) and other six to the para positions of the phenolate group of the ligand (R). Thus, 2 could be exploited to build up supramolecular self-assembling systems used as molecular scaffolds for applications in catalysis and material science. 2 R' R i Pr Ti 1 R' R' R R H 2 R R' R R' R R' Ti Ti R' 2 R R' R' R R R and/or R' = Here we will present the effective synthesis of 2 derivatives bearing pyrenes moieties in different positions and with different linkers, together with their characterization and stability studies and preliminary results related to their applications as multistage redox systems and receptors for C 60. 3,4 Triphenolamines are highly modular tetradentate molecules that effectively coordinate to transition metal ions 1. Their highly modular nature allows to obtain a large family of metal transition complexes that have been used as effective catalysts in different processes such as polymerization 2, oxygen transfer reactions 3 and C 2 fixation 4. Scheme 1 Here we present a novel protocol for the synthesis of 1 based on a three-fold Suzuki coupling starting from the iodo derivative 2 and 3-formylphenylboronic acid. The -protected ligand 2 can be effectively synthesized via three-fold reductive amination of commercially available 2-iodophenol. Different functionalizations in meta position of the peripheral aromatic ring can be exploited to tune the properties of the ligands and the corresponding complexes, such as solubility in different solvents, or to insert new reactive moieties for new applications in catalysis and molecular recognition. In particular, we will present the introduction of azide, hydroxo and formyl groups that can be used for the introduction of multiple and ordered functions via click chemistry. Acknowledgements: We thank Fondazione CARIPAR Progetti di Eccellenza 2011 (ano-mode) and CST Action CM1005 Supramolecular Chemistry in Water for financial support. Acknowledgements: We thank Fondazione CARIPAR Progetti di Eccellenza 2011 (ano-mode) and CST Action CM1005 Supramolecular Chemistry in Water for financial support. [1] Mba, M.; Zonta, C.; Licini, G. Dalton Trans. 2009, Bernardinelli, G.; Seidel, T. M.; Kundig, E. P.; Prins, L. J.; Kolarovic, A.; Mba, M.; Pontini, M.; Licini, G. Dalton Trans. 2007, [2] Lehn, J. M. PAS 2002, 99, Lehn, J. M. Chem Soc. Rev. 2007, 36, 151. [3] Lionetti, D.; Medvecz, A. J.; Ugrinova, V.; Guzman, M. Q.; oll, B. C.; Brown. S. Inorg. Chem. 2010, 49, [4] Fujii, S.; Morita, T.; Kimura, S. Langmuir 2008, 24, Hwang, Y. L.; Hwang, K. C. Fullerene Sci. Technol. 1999, 7, 437. Sluch, M. I.; Samuel, I. D. W.; Petty, M. C. Chem. Phys. Lett. 1997, 280, 315. [1] Licini, G.; Mba, M.; Zonta, C. Dalton Trans. 2009, 27, [2] Kim, Y.; Jnaneshwara, G. K.; Verkade, J. G.; Inorg. Chem, 2003, 42, b) Gendler, S; Segal, S.; Goldberg, I.; Goldschmidt, Z.; KoI, M. Inorg. Chem. 2006, 45, c) Chmura, A. J.; Chuck, C. J.; Davidson, M. G.; Jones, M. D.; Lunn M. D. BuII, S. D.; Mahon, M. F. Angew Chem Int. Ed. 2007, 46, d) Chmura, A. J.; Davidson, M. G.; Frankis, C. J. ; Jones, M. D.; Lunn, M. D. Chem Commun 2008, 11, [3] a) Mba, M.; Prins, L. J.; Licini, G. rg. Lett. 2007, 9, 21-24; b) Mba, M.; Pontini, M.; Lovat, S.; Zonta, C.; Bernardinelli, G.; Kandig, P. E.; Licini, G. Inorg. Chem. 2008, 26, c) Romano, F.; Linden, A.; Mba, M. Zonta, C.; Licini, G. Adv. Synth. Catal. 2010, 352, [4] Whiteoak, C. J.; Gjoka, B.; Martin, E.; MartÍnez Belmonte, M.; Benet-Buchholz, J.; Zonta, C.; Licini, G.; Kleij, A. W. Inorg. Chem. 2012, 51, PSTERS
56 PSTERS Poster 81 Mechanistic Insights Into Water xidation Catalyzed by Ir-Cp* Complexes Arianna Savini, a * Alberto Bucci, a Gianfranco Bellachioma, a Luca Rocchigiani, a Cristiano Zuccaccia, a Antoni Llobet, b Alceo Macchioni a Poster 82 Dehydrogenation of Ammonia-Borane Catalyzed by Palladium and Ruthenium Complexes Andrea Rossi, a,b * Andrea Rossin, a Maurizio Peruzzini, a Fabrizio Zanobini a a Department of Chemistry, University of Perugia, Via Elce di Sotto 8, Perugia, Italy; b Institute of Chemical Research of Catalonia, Avinguda Països Catalans 16, Tarragona, Spain; The realization of an efficient apparatus for artificial photosynthesis is strongly hampered by the difficulty of oxidizing water. Several transition metal complexes have been successfully applied as catalysts for water oxidation and those based on iridium attracted much attention in the last five years because they showed remarkable performance both in terms of TF and T. 1 ur group has contributed to the development of new iridium-based organometallic catalysts for water oxidation. 2 Specifically, [Cp*Ir(bpy)Cl]Cl (1, bpy = 2,2 -bipyridine), Cp*Ir(bzpy) 3 (2, bzpy = 2-benzoylpyridine) and [Cp*Ir(H 2) 3]( 3) 2 (3) showed to be competent catalysts using cerium ammonium nitrate (CA) as a sacrificial oxidant, added in a large excess with respect to the catalyst. This contribution deals with the results of our studies on the reactions of 1-3 with a small excess of CA, performed by a multiple technique approach and aimed at shedding some light on the reaction mechanism. Three main findings have been obtained: i) an intermediate species Cp*L nir IV H was intercepted by UV-Vis spectroscopy; ii) it was concluded that the last oxidative step is most likely the rate determining step of the catalytic cycle (); iii) measurements on C 2 formation indicated that catalyst degradation occurs parallel to oxygen evolution, with a minor extent at high concentration of CA. a Consiglio azionale delle Ricerche, Istituto di Chimica dei Composti rganometallici (ICCM-CR) Via Madonna del Piano 10, Sesto Fiorentino (FI), Italy; b Dipartimento di Chimica 'Ugo Schiff', Università di Firenze, via della Lastruccia 3-13, Sesto Fiorentino (FI), Italy; The increasing quest for efficient and safe hydrogen reservoirs has led to an enormous growth of the hydrogen storage research field in recent years. As far as chemical storage is considered, one of the most promising materials is ammoniaborane (H 3 BH 3, AB, 19.6 wt.% H). 1 Homogeneously-catalyzed AB dehydrogenation is the path that the organometallic chemist can follow to exploit AB as hydrogen storage material. Many transition metal complexes have been proposed as possible catalysts. 2 Recent work in our laboratory has been focused on the Palladium(II) PCP pincer complex [( tbu PCP)Pd(H 2)]PF 6 [1, tbu PCP = 2,6-C 6H 3(CH 2P t Bu 2) 2, ] and on the P 3 Ruthenium(II) hydrides ( 4 -P 3)Ru(H) 2 (2) and [( 4 -P 3)Ru(H)( 2 -H 2)]BAr Cl 4 [3, P 3 = (CH 2CH 2PPh 2) 3, ]. 1 leads to AB oligomerization and formation of spent fuel of general formula cyclo-[bh 2-H 2] n (n = 2,3) as reaction byproducts; one H 2 equivalent is released per AB equivalent. 3 Both 2 and 3 produce borazine as a spent fuel, and a total amount of two H 2 equivalents per AB equivalent. All the processes have been followed through multinuclear ( 31 P, 1 H, 11 B) variable temperature MR spectroscopy; kinetic measurements on the hydrogen production rate and the relative rate constants have also been carried out, along with kinetic isotope effects measured on the deuterated AB analogues (BH 3 D 3, BD 3 H 3, BD 3 D 3). Finally, the reaction mechanism in all cases has been analyzed through a DFT modeling at the M06//6-31+G(d,p) level of theory, with the aim of providing a rationale for the dehydrogenation process. [1] a) Sala, X.; Romero, I.; Rodríguez, M.; Escriche, L.; Llobet, A. Angew. Chem. Int. Ed., 2009, 48, b) Laia, W.; Du, P. Energy Environ. Sci., 2012, 5, c) Limburg, B.; Bouwman, E.; Bonnet, S. Coord. Chem. Rev., 2012, 256, e) Hetterscheid, D. G. H.; Reek, J. H. Angew. Chem. Int. Ed., 2012, 51, [2] a) Savini, A.; Bellachioma, G.; Ciancaleoni, G.; Zuccaccia, C.; Zuccaccia, D.; Macchioni, A. Chem. Commun., 2010, 46, b) Savini, A.; Belanzoni, P.; Bellachioma, G. Zuccaccia, C.; Zuccaccia, D.; Macchioni, A. Green Chem., 2011, 13, c) Savini, A.; Bellachioma, G.; Bolaño, S.; Rocchigiani, L.; Zuccaccia, C.; Zuccaccia, D.; Macchioni, A. ChemSusChem, 2012, 5, d) Bucci, A.; Savini, A.; Rocchigiani, L.; Zuccaccia, C.; Rizzato, S.; Albinati, A.; Llobet, A.; Macchioni, A. rganometallics, 2012, 31, XRD structures of 1 and 2. [1] Staubitz, A.; Robertson, A. P. M.; Manners, I. Chem. Rev. 2010, 110, [2] Alcaraz, G.; Sabo-Etienne, S. Angew. Chem. Int. Ed. 2010, 49, [3] Rossin, A.; Bottari, G.; Lozano, A.; Paneque, M.; Peruzzini, M.; Rossi, A.; Zanobini, F. Dalton Trans. 2013, 42, 3533.
57 Poster 83 rganometallic Iridium Catalysts Based on Pyridinecarboxylate Ligands for the xidative Splitting of Water Alberto Bucci, a * Arianna Savini, a Luca Rocchigiani, a Cristiano Zuccaccia, a Silvia Rizzato, b Alberto Albinati, b Antoni Llobet, c Alceo Macchioni a a Dipartimento di Chimica, University of Perugia, Via Elce di Sotto 8, Perugia (Pg), Italy; b Dipartimento di Chimica, University of Milano, Via Golgi 19, Milano (MI), Italy; c Institute of Chemical Research of Catalonia, Avinguda Paı sos Catalans 16, Tarragona, Spain; Aimed at producing renewable solar fuels from cheap and abundant reagents (H 2 and C 2), artificial photosynthesis appears to be a promising solution to the energetic problem of our days. It involves several and complicated processes that have to be properly interfaced between them, but the real bottleneck seems to be the development of an efficient catalytic pool for water oxidation. 1 Ir(III)-Cp* (1,2,3,4,5 pentamethylcyclopentadienyl) 2 organometallic complexes imposed to the attention of the scientific community as efficient molecular catalysts for water oxidation. 3 evertheless, the fastest catalyst reported to date is a ruthenium complex bearing a pyridinecarboxylate ligand. 4 For this reason we decided to synthesize and test 1-4 iridium catalysts containing pyridinecarboxylate ligands (, left). 5 Their activity was evaluated by means of different experimental techniques, using Ce +4 as a sacrificial oxidant. Although they show similar TF LT values (long range TF, between min -1 ), TF i values (initial TF) are very different (, right), reaching 287 min -1 for 1a (under optimized conditions). This value is the highest ever reported for an iridium catalyst, and it is about four times higher than the one of Cp*Ir(ppy)Cl (ppy = 2-phenylpyridine), which is considered a benchmark in the literature. 2a [1] Balzani, V., Credi, A. and Venturi, M., ChemSusChem, 2008, 1, 26; b) Meyer, T. J. Acc.Chem. Res., 1989, 22, 163. [2] a) Hull, J. F.; Balcells, D.; Blakemore, J. D.; Incarvito, C. D.; Eisenstein,.; Brudvig, G. W.; Crabtree, R. H. J. Am. Chem. Soc.2009,131, ; b) Savini, A.; Bellachioma, G.; Ciancaleoni, G.; Zuccaccia, C.; Zuccaccia, D.; Macchioni, A. Chem. Commun. 2010, 46, [3] Laia, W.; Du, P. Energy Environ. Sci. 2012, 5, ; Limburg, B.; Bouwman, E.; Bonnet, S. Coord. Chem. Rev. 2012, 256, Liu, X.; Wang, F. Coord. Chem. Rev. 2012, 256, [4] Duan, L.; Bozoglian, F.; Mandal, S.; Stewart, B.; Privalov, T.; Llobet, A.; Sun, L. at. Chem. 2012, 4, [5] Bucci, A.; Savini, A.; Rocchigiani, L.; Zuccaccia, C.; Rizzato, S.; Albinati, A.; Llobet, A.; Macchioni, A. rganometallics 2012, 31, Poster 84 Bipyridine-type rganometallic Complexes Functionalize Glassy Carbon Cunfa Sun, Federico Franco, Claudio Cometto, Roberto Gobetto, Carlo ervi* Department of Chemistry, University of Turin, via P. Giuria 7, 10125, Turin, Italy, In the past research, silica and alumina (in all their forms) as supports for catalysts have been mostly studied and employed, however, much less attention has been paid to the synthesis and study of catalysts containing transition metals on non-oxide solids. As one of them, carbon is a very interesting low-cost material, and very favourable for electrodes manufacturing. We already bound intact Ru and Ir organometallic molecules to carbon electrode surface by means of electrochemical techniques 1 pioneered by Saveant and co-workers. 2 The present communication aims to extend the technique to Re organometallic complexes of the type (bpy)re(c) 3Cl. Interest in this class of compounds lies in their activity towards selective C 2 photo- and electro-reduction, via a reductive quenching mechanism. 3 The reduction of C 2 emission and the quest for renewable energy are top priorities on the world s strategic research agenda. In the C 2 Re-photocatalyzed reduction to C, two 1e electron transfer processes are likely involved, and the use of bimetallic system apparently gave some advantages over the mononuclear Re complex. 4 However, it is not fully clear whether the presence of a second Re unit is needed for only supplying electrons or is involved in the formation of a real Re-C 2-Re bimetallic intermediate. The functionalization of intact organometallic complexes over carbon surfaces has thus the advantage to simplify the study of the photocatalytic conversion of C 2 to C, since the employment of a potentiostat allows to avoid to use Sacrificial Reagents in the solution. The complex herein presented shows an increased activity towards C 2 electrochemical reduction with respect the standard (bpy)re(c) 3Cl in both homogeneous and heterogeneous (i.e. chemically bonded to Glassy Carbon electrode surface). [1] Sandroni, M.; Volpi, G.; Fiedler, J.; Buscaino, R.; Viscardi, G.; Milone, L.; Gobetto, R.; ervi, C. Cat. Today 2010, 158, 22. [2] Allongue, P.; Delamar, M.; Desbat, B.; Fagebaume,.; Hitmi, R.; Pinson, J.; Savéant, J.-M. J. Am. Chem. Soc. 1997, 119, 201. [3] Morris, A. J.; Meyer, G. J.; Fujita, E. Acc. Chem. Res. 2009, 42, [4] Bruckmeier, C.; Lehenmeier, M. W.; Reithmeier, R.; Rieger, B.; Herranz, J.; Kavakli, C. Dalton Trans. 2012, 41, PSTERS
58 PSTERS Poster 85 ew Aminomethyl-Substituted Ferrocenes and Derivatives: Efficient Synthetic Routes, and Structural and Electrochemical Characterization Poster 86 Synthesis and Electrochemical Study of Re(I) and Mo(0) Complexes with Polypyridyl Ligands for Photo- and Electrocatalytic Reduction of C 2 ejib Dwadnia,* a,b Fatima Allouch, a Julien Roger, a adine Pirio, a Ridha Ben Salem, b Jean-Cyrille Hierso* a Federico Franco,* Cunfa Sun, Claudio Cometto, Roberto Gobetto, Carlo ervi a b Université de Bourgogne, ICMUB UMR-CRS avenue Alain Savary, Dijon, France; Université de Sfax, Faculté des Sciences, LCP UR 11ES74 Sfax 3038, Tunisia Functionalized ferrocene derivatives are molecular edifices for which a wide range of useful applications exist, particularly in close relationship with homogeneous catalysis, electrochemistry, material and polymer sciences, and biomedical research. 1 Driven by transition-metal-catalyzed applications, the synthesis of ferrocene derivatives incorporating atoms with donor bonding abilities such as phosphorus atoms has attracted much attention. 2,3 itrogensubstituted ferrocenes have been comparatively much less developed, even though a significant amount of works and molecules have been reported since the 1960 s. We report herein the straightforward syntheses of a variety of (aminomethyl)-substituted ferrocenes and parent compounds: (iminomethyl) ferrocenes, aza-ferrocenophanes and diferrocenylamines that can be selectively synthesized from reductive amination of 1,1'-diformylferrocene or formylferrocene. 4 The optimized one or two-steps reactions have delivered 13 new compounds, isolated in 65 to 97% yields. X-ray structure of representative members of these ferrocene derivatives families have evidenced the preferred conformation adopted by ferrocene backbones. 15 MR measurements on (aminomethyl)-substituted compounds established benchmark values ranging from 70 to 95 ppm (nitromethane δ = 0 ppm). 4 The cyclic voltammetry of these species evidences two clearly distinct oxidation potential related to the Fe(II) center and the nitrogen-containing function (Figure1) Department of Chemistry, University of Turin, via P. Giuria 7, 10125, Turin, Italy; In recent years, the photo- and electrochemical conversion of C 2 to higher-energy products has been improved by employing transition metal coordination compounds with polypyridyl ligands (e.g. Ru, s, Re, Mn 1,2 ), in the form of molecular or supramolecular organometallic catalysts. In this perspective, our research has mainly focused on the synthesis of a series of novel Re(I)-carbonyl diimine complexes, to be efficiently used as catalysts in both photo- and electrocatalysis for C 2 reduction. In more detail, this new class of compounds is characterized by the presence of common polypyridyl ligands covalently attached to the highly fluorescent PI cromophore (-(diimine)-4-(1- piperidinyl) naphthalene-1,8- dicarboximide), which revealed to be able to provide a huge excited state lifetime enhancement in a Re(I) charge-transfer complex. 3. This feature may play a key role in the process of catalytic C 2 reduction (especially in photocatalysis). The spectroscopic characterization (optical and MR) of the new samples was followed by the study of their electrochemical behaviour either in inert atmosphere and in presence of C 2, which was finally compared with that of Re(C) 3(bipy)Cl, taken as a reference compound. 4 Photocatalytic measurements are under progress. n the other hand, looking at a practical use of these systems, the usage of quite abundant first and second row transition metals instead of rare ones is very attractive. For example, to our knowledge there are no reports about the use of tetracarbonyl Mo(0) complexes for the same purpose. This reason lead us to synthesize also a series of [Mo(C) 4(L)] complexes (L = 2,2 -bipyridyl and derivatives), testing them for electrochemical reduction of carbon dioxide. ur first results are quite promising, showing certain activity and selectivity in reducing C 2 to C. [1] Bourrez, M.; Molton, F.; Chardon-oblat, S.; Deronzier, A.; Angew. Chem. 2011, 50, [2] Morris, A.J.; Meyer, G.J.; Fujita, E.; Acc. Chem. Res. 2009, 42, [3] Yarnell, J. E.; Deaton, J. C.; McCusker, C. E.; Castellano, F.; Inorg. Chem. 2011, 50, [4] Johnson, F. P. A.; George, M. W.; Hartl, F.; Turner, J. J.; rganometallics 1996, 15, Electrochemical analyses have been achieved in Pr. D. Lucas group and X-Ray analysis done by Dr. H. Cattey (UMR-CRS 6302, Dijon). [1] Atkinson, R. C. J.; Gibson, V. C.; Long,. J. Chem. Soc. Rev. 2004, 33, 313. [2] Roy, D.; Mom, S.; Beaupérin, M.; Doucet, H.; Hierso, J.-C. Angew. Chem. Int. Ed. 2010, 49, [3] Roy, D.; Mom, S.; Royer, S.; Lucas, D.; Hierso, J.-C.; Doucet, H. ACS Catalysis 2012, 2, [4] Dwadnia,.; Allouch, F.; Hierso, J.-C. et al. rganometallics 2013, doi: /om400317s.
59 Poster 87 Ion pairing in cationic HC and AC gold(i) 2 --alkyne complexes Leonardo Belpassi, a Luca Biasiolo,* a,b Giovanni Bistoni, a,c Gianluca Ciancaleoni, a Alceo Macchioni, c Francesco Tarantelli, a,c Daniele Zuccaccia b Poster 88 Controlled Self-Assembly of Peptidic Au(I)-Metalloamphiphiles through Cooperative Interactions Benedict Kemper,* Yana R. Hristova, Pol Besenius a Istituto di Scienze e Tecnologie Molecolari del CR (CR-ISTM), c/o Dipartimento di Chimica, Università degli Studi di Perugia, I-06123, Perugia, Italy; b Dipartimento di Chimica, Fisica e Ambiente, Università di Udine, Via Cotonificio 108, I Udine, Italy; c Dipartimento di Chimica, Università degli Studi di Perugia Via Elce di sotto 8, I-06123, Perugia, Italy; Gold(I) cationic complexes of general formula [LAu + X - ] [L = AC (itrogen-acyclic-carbene) or HCs (- Heterocyclic Carbenes), X - = weakly coordinating anion] are successfully employed as catalysts in a large variety of organic reactions involving the activation of unsaturated carbon-carbon bonds. 1 A key role in such reactions is played by the counterion. We have studied the ion pair structure in solution of [HC-Au( 2-3-hexyne)]BF 4 and [AC-Au( 2-3- hexyne)]bf 4 by E MR spectroscopy and relativistic DFT calculation. In our previous work, 2 two main orientations were observed for unsaturated HC ligands: one with the anion close to the carbene backbone (A, most populated) and another with the anion close to the 3-hexyne (B). Here we focus on the effect of different carbenes on the ion pair structure, comparing the aromatic HC (1BF 4) with 5 different ligands: a non aromatic HC (2BF 4), a polycyclic ligand with an extended aromatic system (3BF 4) and three different AC (4BF 4, 5BF 4 and 6BF 4). For 2BF 4, the A:B ratio (observed with E MR spectroscopy) remains almost the same as for 1BF 4, whilst the ion pair structure of the 3BF 4 becomes mainly non-- specific, with a slight preference for the orientation B. Both cases can be explained analyzing the DFT Coulomb potential map, that shows an attractive region on the backbone of 2BF 4 and a flat weak potential around the whole 3BF 4. An interesting result was obtained for 4BF 4 that shows a strong attractive region close to the two -H that makes the IP 100% specific for the orientation A (figure beside). 5BF 4 shows a less specific ion pair due to the presence of only one -H on the back. For the 6BF 4 the -H group on the arm of the carbene introduce a third ion pair configuration, strongly stabilized by the hydrogen bond between the hydroxyl and the anion. rganic Chemistry Institute and CeTech, Heisenbergstraße 11, Westfälische Wilhelms-Universität Münster, D Münster, Germany, The aim of the work presented herein is to couple Au(I) species to small peptide building blocks in order to prepare new metalloamphiphilic complexes as supramolecular monomers (). The peptide sequences are designed in a fashion that prevents the spontaneous formation of aggregates. The non-covalent polymerisation process only becomes thermodynamically favourable through the additional formation of aurophilic interactions. 1 The cooperative effects dictating the self-assembly of these supramolecular polymers in water 2 and their photoluminescent properties will be investigated. 3,4 H H R R H H R R H H R R Au + Au + Ligand Ligand : Cooperative interactions during self-assembly. 19 F H HESY Figure 2. [HC-Au( 2-3-hexyne)]BF4 and [AC-Au( 2-3-hexyne)]BF4 complexes [1] Hashmi, A. S. K. Chem. Rev. 2007, 107, [2] (a) Salvi,.; Belpassi, L.; Zuccaccia, D.; Tarantelli, F.; Macchioni, A. J. rganomet. Chem. 2010, 695, (b) Zuccaccia, D.; Belpassi, L.; Rocchigiani, L.; Tarantelli, F.; Macchioni, A. Inorg. Chem., 2010, 49, (c) Zuccaccia, D.; Belpassi, L.; Tarantelli, F.; Macchioni, A. J. Am. Chem. Soc., 2009, 131, (d) Ciancaleoni, G.; Belpassi, L.; Tarantelli, F.; Zuccaccia, D.; Macchioni, A. Dalton Trans 2013, 42, [1] Schmidbaur, H.; Schier, A. Chem. Soc. Rev. 2012, 41, [2] von Gröning, M.; de Feijter, I.; Stuart, M. C. A.; Voets, I. K.; Besenius, P. J. Mater. Chem. B 2013, 1, [3] Yam, V. W.-W.; Cheng, E. C.-C. Chem. Soc. Rev. 2008, 37, [4] Lima, J. C.; Rodríguez, L. Chem. Soc. Rev. 2011, 40, PSTERS
60 PSTERS Poster 89 Artificial Leaf Towards Photoactive Electrodes for Hydrogen Production from Water Poster 90 Bifunctionalized Re(I) Complexes as Luminescent Probes for Bioconjugation René Becker,* Joost Reek Elia Matteucci,* Andrea Baschieri, Stefano Stagni, Letizia Sambri Van t Hoff Institute of Molecular Sciences, Universiteit van Amsterdam, The etherlands; * Dipartimento di Chimica Industriale Toso Montanari, viale Risorgimento, Bologna, Italy; As a possible sustainable alternative to the current fossil fuel economy, the production of hydrogen from water by means of solar energy is currently investigated by a large number of scientists. The first functional integrated device that could split water using light (colloquially called an artificial leaf) was shown by Khaselev and Turner. 1 To improve device efficiency and durability, the use of homogeneous catalysts immobilized on a suitable substrate is studied. As opposed to active heterogeneous layers, homogeneous building blocks offer the advantage of having easily tunable properties and a well-defined catalytic character. Using the two inherent constraints of photocatalytic water splitting (the sun s photon flux and water splitting redox potentials) these catalysts can be straightforwardly optimized. ctahedral Re(I) complexes of the general formula fac-[re(^)(c) 3L] +, where ^ represents a diimine-type ligand, constitute of promising class of luminescent probes for biological systems. 1 Here, we report the synthesis and characterization of a new class of bifunctionalized Re(I) complexes containing an unconventional diimine ligand (^) decorated both with a pendant biotin and a polar subtituent, in order to achieve the formation of luminescent probes for avidin with improved water solubility. (Scheme 1). Sankey diagram for matching of photon flux and turnover frequencies. Scheme 1 [1] a) Zhao, Q.; Huanga, C.; Li, F. Chem. Soc. Rev. 2011, 40, ; b) Choi, A. W.-T.; Louie, M.-W.; Li, S. P.-Y.; Liu, H.-W.; Chan, B. T.-.; Lam, T. C.-Y.; Lin, A. C.-C.; Cheng, S.-H.; Lo, K. K.-W. Inorg. Chem. 2012, 51, and cited references. Figure 2. Limiting cases of electron transfer between catalyst and a suitable substrate. [1] Khaselev,.; Turner, J. A. Science 1998, 280, 425.
61 Poster 91 A 33 S MR-Based Assay to Monitor Transmembrane Sulfate Transport Across Synthetic Phospholipid Bilayers Louise E. Karagiannidis,* a athalie Busschaert, a Marco Wenzel, a Cally J. E. Haynes, a Philip G. Young, Jack K. Clegg, b Mohan Bhadbhade, b Damjan Makuc, a Katrina A. Jolliffe, b Janez Plavec, c Philip A. Gale a Poster 92 Phosphine xide-based Supramolecular Complexes from Phosphine Donor Malaichamy Sathiyendiran,* Bhaskaran Shankar, Palani Elumalai, Virendar Singh, Dhanraj T. Masram Department of Chemistry, University of Delhi, Delhi-7, India; a Chemistry, University of Southampton, Southampton, UK, S17 1BJ; b School of Chemistry, The University of Sydney, SW, AU, 2006; c ational Institute of Chemistry, Ljubljana, SI, 1001 The transport of sulfate anions across cell membranes is central to many biological processes, 1 and is facilitated by specialised membrane proteins. However, the malfunction of these proteins can lead to the misregulation of sulfate concentrations, a contributing factor to illnesses such as Alzheimer s disease. 2 Accordingly, there is an ever-present interest in the design and synthesis of synthetic small molecules, which can act as transmembrane sulfate transporters. Transmembrane sulfate transport is particularly challenging due to the high hydrophilicity of the anion. 3 Here we report a novel MR technique, which is used to directly monitor the transport of sulfate anions across synthetic phospholipid bilayers. This technique gives a definitive yes/no result, allowing the sulfate transport ability of a particular receptor to be investigated. Using the developed 33 S MR method, it was possible to verify that some tren-based (thio)ureas 4 and cyclic peptide-based cryptands 5,6 are able to accomplish the challenging task of sulfate transport. ver the past three decades, significant research interest has been shown in discrete supramolecular coordination complexes (SCCs), because of their properties and potential applications in many fields. 1 The synthesis of SCCs by coordination-driven self-assembly, using predesigned transition metal based acceptors and organic donor precursors, is well established. Recent developments in this field are focused on making complex SCCs, SCCs with functional units, and finding a one-pot strategy for multicomponent assembly. In donor ligands, neutral nitrogen () units are widely used as either the whole or part of the organic structure in SCCs. Attempts are being made to use other neutral Lewis base donor in place of the -donor ligands. As a continuation of the research on Re(I)-based SCCs previously reported, 2-6 the first examples of neutral -donor, from phosphine oxide, bridged SCCs have been synthesised and are reported herein (Scheme 1). Scheme 1 [1] Busschaert,.; Gale, P. A. Angew. Chem. Int. Ed. 2013, 52, [2] Markovich, D. Physiol. Rev. 2001, 81, [3] Marcus, Y. J. Chem. Soc. Faraday Trans. 1991, 87, [4] Busschaert,.; Wenzel, M.; Light, M. E.; Iglesias-Hernández, P.; Pérez-Tomás, R.; Gale, P. A. J. Am. Chem. Soc. 2011, 133, [5] Young, P. G.; Clegg, J. K.; Bhadbhade, M.; Jolliffe, K. A. Chem. Commun. 2011, 47, 463. [6] Young P. G.; Jolliffe, K. A. rg. Biomol. Chem. 2012, 10, [1] Leininger, S.; lenyuk, B.; Stang, P. J. Chem. Rev. 2000, 100, 853. [2] Shankar, B.; Elumalai, P.; Hussain, F.; Sathiyendiran, M. J. rganomet. Chem. 2013, 732, 130. [3] P. Rajakannu, P.; Elumalai, P.; Hussain, F.; Sathiyendiran, M. J. rganomet. Chem. 2013, 725, 1. [4] Rajakannu, P.; Shankar, B.; Yadav, A.; Shanmugam, R.; Gupta, D.; Hussain, F.; Chang, C. H.; Sathiyendiran, M.; Lu, K. L rganometallics, 2012, 30, [5] Shankar, B.; Hussain, F.; Sathiyendiran, M. J. rganomet. Chem. 2012, 719, 26.[6] Gupta, D.; Rajakannu, P.; Shankar, B.; Shanmugam, R.; Hussain, F.; Sarkar, B.; Sathiyendiran, B. Dalton Trans. 2011, 40, PSTERS
62 PSTERS Poster 93 Copper Metallohydrogels: Self-Assembly and Applications in Catalysis Poster 94 Bifunctional -Heterocyclic Carbene (HC) Complexes and their Catalytic Evaluation M. Tena-Solsona, César A. Angulo-Pachón,* B. Escuder, J. F. Miravet Abir Sarbajna,* a Biswajit Saha, a Jitendra K. Bera a Dep. Química Inorgànica i rgànica, Universitat Jaume I, Castelló, Spain; a Department of Chemistry, IIT Kanpur, Kanpur , India; In recent years, the self-assembly of compounds have gained more and more interest 1 due to their attractiveness in the fields of smart materials, drug delivery, and catalysis. 2 on-covalent interactions are the driving forces of the molecular self-assembly of compounds such as small peptides. These supramolecular interactions are reversible and may be induced by external or internal stimuli. 3 The design of molecular building units becomes crucial for the structure, properties and function of the resulting assemblies. 4 We have designed a new supramolecular metallohydrogelator (figure 1) presenting alternating phenylalanine/aspartic acid residues. The addition of cooper (II) chloride to a basic solution of 1 leads to the formation of stable light blue and translucent metallohydrogel likely by the interaction of metal-ligand between copper(ii) and aspartic acid moieties. 5 Besides elucidate their structure gelation properties and their aggregation mechanisms, we want to study if the formed Cu 2+ containing nanostructures can function as an asymmetric catalyst for Diels Alder cycloaddition between cyclopentadiene and aza-chalcone 6 (figure 1). Early organometallic catalysts contained a metal which was thought to be the active centre where as ligands provided sterically-defined binding sites through association or dissociation for the substrate to bind and undergo transformation. However, with the recent advancements in catalysis, it has been widely recognized that subtle and judicious designing of ligands enable them to participate actively in bond breaking and making processes during the catalytic cycle, thus increasing the tolerance, efficiency and selectivity of the catalyst. 1 -Heterocyclic Carbenes (HC s) have gradually emerged as superior counterparts to phosphines over the years due to their robust nature and tunable steric and electronic properties. 2 This work focuses on the incorporation of bifunctional HC s on transition metals and their effect in homogeneous catalysis. 3 Acknowledgements: We thank Spanish Ministry of Economy and Competitiveness (grants CTQ and CTQ ), Universitat Jaume I (grant P1.1B ) and CST Action CM1005 for financial support. M.T.S. thanks Spanish Ministry of Education, Culture and Sports for the FPU predoctoral fellowship (AP ). [1] Kameta,.; Minamikawa, H.; Masuda, M. Soft Matter 2011, 7, [2] Frusawa, H.; Fukagawa, A.; Ikeda, Y.; Araki, J. A.; Ito, K.; John, G.; Shimizu, T. Angew. Chem., Int.Ed. 2003, 42, 72. [3] (a) Hirst, A. R.; Escuder, B.; Miravet, J. F.; Smith, D. K. Angew. Chem. Int. Ed. 2008, 47, (b) Tomasini, C.; Castellucci,. Chem. Soc. Rev. 2013, 42, 156. [4] Measey, T. J.; Schweitzer-Stenner, R.; Sa. V.; Kornev. K. Macromolecules 2010, 43, [5] Tam, A. Y-Y.; Yam, V. W-W. Chem. Soc. Rev. 2013, 42, [6] Jin, Q.; Zhang, L.; Cao, H; Wang, T.; Zhu, X.; Jiang, J.; Liu, M. Langmuir 2011, 27, [1] oyori, R.; Yamakawa, M.; Hashiguchi, S. J. rg. Chem., 2001, 66, [2] olan, S. P. -Heterocyclic Carbenes in Synthesis; (Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim) [3] (a) Daw, P.; Sinha, A.; Rahaman, S. M. W.; Dinda, S.; Bera, J. K. rganometallics, 2012, 31, (b) Unpublished Results.
63 Poster 95 Synthesis, Characterisation, and catalytic Activity of ovel Pd(II) Complexes Containing 4-Substituted Bis(Pyrazolyl)Methane Ligands Poster 96 MW Buchwald Amination as a Key Step in the Synthesis of a new Series of Psensitizers for DSC Corrado Di icola, a Fabio Marchetti, b Claudio Pettinari, a Marcello Crucianelli, c Camilla Lelii,* c Alessandra Crispini d a School of Pharmac and b School of Science and Technology, y, Università degli Studi di Camerino, via S. Agostino 1, Camerino MC, Italy; c Dipartimento di Scienze Fisiche e Chimiche, Università dell Aquila, via Vetoio, I Coppito, AQ, Italy; d Centro di Eccellenza CEMIF.CAL-LASCAMM, CR-ISTM (Unità della Calabria, Dipartimento di Chimica), Dipartimento di Scienze Farmaceutiche, Edificio Polifunzionale, Università della Calabria, I Arcavacata di Rende, CS, Italy; Among the wide range of bidentate chelating ligands currently used in metal coordination chemistry, bis(pyrazolyl)alkanes are one of the most fascinating family of stable and flexible ligands: they are isoelectronic and isosteric with the well-known bis(pyrazolyl)borates, and were first synthesized by Trofimenko in the seventeen of the last century. 1 The coordinating properties of bis(pyrazol-1-yl)alkanes can be varied over wide range by introduction of various substituents into the pyrazole rings which are able to modify steric and electronic properties. 2 Their metal coordination chemistry with main group and transition metals has been mainly developed in the last twenty years 2 affording a number of transition metal systems with novel interesting properties in the fields of catalysis. 3,4 Here we report novel bis(pirazolyl)methane ligands bearing 4-substituents () and their coordination chemistry toward PdCl 2 and Pd(Ac) 2 acceptors. Additionally, some selected derivatives have also been tested for their potential catalytic activity in Suzuki-Miyaura cross-coupling reactions. Davide Saccone,* Claudia Barolo, Roberto Buscaino, Guido Viscardi Department of Chemistry, University of Torino, via Pietro Giuria 7, Torino 10125, Italy; Development of new sensitizers for DSCs 1,2 is a constant challenge to achieve better harnessing of solar energy in innovative photovoltaic devices. In metal-free sensitizers, the triarylamine moiety has a key role as electron donor group. The study of relative synthesis could help the research to obtain triarylamine 3 compounds in a easier, faster, more selective and reproducible way. We studied a synthetic path to obtain these compounds by a Buchwald 4 amination using microwave 5 in order to decrease reaction time and to increase yield compared to a synthetic approach based on conventional heating. 6 Br Br I I Me Me Me Me Me Me L 1 L 2 L 3 Figure 2 [1] Trofimenko, S. J. Am. Chem. Soc. 1970, 70, [2] Pettinari, C.; Pettinari, R. Coord. Chem. Rev. 2005, 249, [3] Joshi, V. S.; andi, M.; Zhang, H.: Haggerty, B. S.; Sarkar, A. Inorg. Chem, 1993, 32, [4] Field, L. D.; Messerle, B. A.; Rehr, M.; Soler, L. P.; Hambley, T. W. rganometallics 2003, 22, Scheme 1 [1] Kanaparthi, R. K.; Kandhadi, J.; Giribabu, L. Tetrahedron 2012, 68, [2] Mishra, A.; Fischer, M. K. R.; Bauerle, P. Angew. Chem. Int. Ed. 2009, 48, [3] Manifar, T.; Rohani, S. Can. J. Chem. Eng. 2004, 82, [4] Yang, B. H.; Buchwald, S. L. J. rganomet. Chem. 1999, 576, [5] Kappe, C. Angew. Chem. Int. Ed. 2004, 43, [6] Adeniji, A.; Twenter, B. M.; Byrns, M. C.; Jin, Y.; Chen, M.; Winkler, J. D.; Penning, T. M. J. Med. Chem. 2012, 55, PSTERS
64 PSTERS Poster 97 uclear Spin-Spin Couplings: Recognition and Understanding of «Through-Space» MR J Constants in rganic and rganometallic Compounds Jean-Cyrille Hierso a,b Poster 98 Synthesis of Phosphine-containing Polymers and their application to Hydroformylation Florence Gayet,* a,b Andrés F. Cardozo, a,b,c Eric Manoury, a,b Carine Julcour, b,c Jean-François Blanco, b,c Henri Delmas, b,c Rinaldo Poli* a,b,d a Université de Bourgogne, Institut de Chimie Moléculaire UMR-CRS 6302, Dijon, France, b Institut Universitaire de France (IUF) In MR the indirect nuclear spin-spin coupling involving very commonly encountered nuclei, such as 1 H, 13 C, 19 F or 31 P, provides conclusive data for compound characterization in solution, using the determination and interpretation of nuclear spin-spin coupling. This electron-mediated nuclear spin coupling, characterized by the J constant, is classically taught as transmitted by unambiguously covalently bonded atoms. Yet, since the 1960 s, experimental and theoretical MR studies have highlighted the existence of scalar J spin couplings operating through clearly nonbonded interactions. These couplings are often called through-space internuclear spin-spin couplings (TS couplings). As presented herein, 1 nonbonded spin couplings ( through-space ) characterized by high magnitude values of J FF, J FX (X =, P, Se, C and H), J PP and J PX (X = Se and C) have been authenticated for compounds such as fluorocyclophanes, fluoronaphthalenes, and coordination complexes of ferrocenyl polyphosphines (). Semi-empirical quantitative relationships have been discovered which show an apparent exponential dependence of the spin coupling intensity with the internuclear distance. 2 In non-covalently bonded interactions, indirect scalar couplings can be frequently observed across the hydrogen bonding of biomolecules and smaller chemical compounds. ur works aim at clarifying such through-space couplings. uclear Spin-Spin Coupling To be or not to be bonded a CRS, LCC (Laboratoire de Chimie de Coordination), 205 route de arbonne, F Toulouse Cedex 4, France; b Université de Toulouse, UPS, IPT, F Toulouse Cedex 4, France; c CRS, LGC (Laboratoire de Génie Chimique), 4 Allée Emile Monso, Toulouse Cedex 4 France ; d Institut Universitaire de France, 103, boulevard Saint Michel, Paris, France; lefin hydroformylation continues to attract interest in view of its industrial importance (oxo process), especially for the conversion of α-olefins to aldehydes with the linear product being preferred. ne of the greatest challenges remains the efficient extension of the rhodium-catalyzed low-pressure process to the higher olefins (> C 4) with total catalyst recovery and low separation costs. The typical precatalyst is Rh(acac)(C) 2/PPh 3 (or other more elaborate mono- or multidentate phosphine donors), then transformed in situ to the active catalyst by syngas. Phosphine ligand grafting on polymers has been one of the most investigated approaches to address this challenge. The effect of the polymer microstructure on the catalytic performance has so far received little attention. n the other hand, the recent phenomenal progress in controlled polymerization makes it possible to build macromolecules with controlled size, architecture, composition and functionality. This therefore gives the opportunity to revisit polymersupported hydroformylation catalysts. The synthesis and characterization of both linear (A) 1 and star-shaped (B) 2 in-chain functionalized polystyrenes with controlled molecular weight and phosphine density by atom transfer radical copolymerization of styrene and styryldiphenylphosphine (SDPP) will be described. The performance of these macroligands in the hydroformylation of a model α-olefin (1-octene) and the dependence of activity and l/b selectivity on the polymer architecture, phosphine density, chain length and other parameters has been evaluated. = B A PPh 2 [1] Hierso, J.-C. Chem. Rev. 2013, under revision process. [2] a) Hierso, J.-C.; Fihri, A.; Ivanov, V. V.; Hanquet, B.; Pirio,.; Donnadieu, B.; Rebière, B.; Amardeil, R.; Meunier, P. J. Am. Chem. Soc. 2004, 126, 11077; b) Hierso, J.-C.; Evrard, D.; Lucas, D.; Richard, P.; Cattey, H.; Hanquet, B.; Meunier, P. J. rganomet. Chem. 2008, 693, 574. [1] Cardozo, A. F.; Manoury, E.; Julcour, C.; Blanco, J.-F.; Delmas, H.; Gayet, F.; Poli, R. ChemCatChem, 2013, 5, [2] Cardozo, A. F.; Manoury, E.; Julcour, C.; Blanco, J.-F.; Delmas, H.; Gayet, F.; Poli, R. Dalton Trans., 2013, 42, 9148
65 Poster 99 Studies of Rhodium Complexation into Phosphine-Containing Latexes Si Chen, a,b Florence Gayet, a,b Eric Manoury, a,b Rinaldo Poli a,b,c a CRS, Laboratoire de Chimie de Coordination, 205, route de arbonne, F Toulouse, France; b Université de Toulouse, UPS, IPT, F Toulouse Cedex 4, France; c Institut Universitaire de France, 103, boulevard Saint Michel, Paris, France Phosphines are common electron donating ligands that can coordinate many important catalytic metals (e.g. Ru, Pd, Rh..) 1 Wilkinson s work revealed the potential of rhodium phosphine catalysts for the hydroformylation reaction of alkenes 2 and this has become the most important industrial homogeneous catalysis process today. 3 An outstanding challenge is that of extending the existing technology which is well adapted to small olefins (propene, butane) to the higher olefins and for this purpose several strategies are being investigated, including the use of polymer-supported phosphines. In this work latexes containing hydrosoluble polymers () that consist of a nanogel core (blue) and flexible amphiphilic arms with a phosphine-containing hydrophophic bloc (green) and a hydrophilic shell (red) have been used as substrates for coordination studies. We will present complexation studies of the [Rh(C) 2(acac)] precatalyst into the particles using different P/Rh ratios and different solvents (i.e. CHCl 3 and toluene) that help swelling the latex core. The investigations confirm that [Rh(C) 2(acac)] is transported across the hydrophilic polymer corona to reach the phosphine sites, trapped at the centre of the particles and provides information about the dynamics of the phosphine exchange within the macromolecule. Poster 100 Antiproliferative Activity of a ew (Arene)Ruthenium(II) Complex on a Model of Breast Cancer Fabio Marchetti, a Corrado Di icola, b Riccardo Pettinari, b Claudio Pettinari, b Maura Montani,* c Gretta Veronica Badillo Pazman, c Augusto Amici, c Giulio Lupidi, b Cristina Marchini c a School of Science and Technology and b School of Pharmacy, Via S. Agostino 1, Camerino (MC), Italy; c School of Bioscience and Biotechnology, Via Madonna delle Carceri, Camerino (MC) Italy.; Following our previous studies, 1 novel (arene)ruthenium(ii) complexes containing neutral chelating nitrogen ligands, with general formula [Ru(arene)(L )Cl]Cl, have been prepared by reacting the ligands L (L in general; in detail, L 1 = bis(pyrazol-1-yl)methane; L 2 = bis(3,5-dimethylpyrazol-1-yl) methane) with some dinuclear organometallic acceptors of ruthenium, such as (para-cymene)ruthenium(ii) dichloride, (benzene)ruthenium(ii) dichloride and (hexamethylbenzene)ruthenium(ii) dichloride. The solid-state structures of these half-sandwich organometallic complexes were determined by X-ray crystallographic studies. 1 Their antiproliferative properties were assessed in vitro and in vivo screening assays and it was found that the Ru(II) complexes exhibit potent antiproliferative activity against different human malignant cancer cells, even in comparison with cisplatin and AMI-A (). Moreover, our data clearly that some Ru(II) complexes are characterized by a strong ability to block cells migration associated with a low toxicity. Swelling by CHCl 3 Acknowledgments: We thank the C2P2 team in Lyon, France: Dr. X. Zang, Dr M. Lansalot, Dr F. D Agosto, Pr. B. Charleux and the AR BIPHASACAT grant for funding. [1] Guinó, M.; Hii, K. K. Chem. Soc. Rev. 2007, [2] sborn, J. A.; Wilkinson, G.; Young, J. F. Chem. Commun. 1965, [3] (a) Tudor, R.; Ashley, M. Platinum Met. Rev. 2007, 51, (b) Tudor, R.; Ashley, M. Platinum Met. Rev. 2007, 51, [1] Marchetti, F.; Pettinari, C.; Pettinari, R.; Cerquetella, A.; Di icola, C.; Macchioni, A.; Zuccaccia, D.; Monari, M.; Piccinelli, F. Inorg. Chem. 2008, 47, PSTERS
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