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Carborane Derivatives with Electron Rich Moieties. Synthesis, Properties and Electronic

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Carborane Derivatives with Electron Rich Moieties. Synthesis, Properties and Electronic Carborane derivatives with electron rich moieties. Synthesis, properties and electronic communication. RADU-ADRIAN POPESCU TESI DOCTORAL Programa de Doctorat en Química Directora: Prof. Clara Viñas Teixidor Departament de Química Facultat de Ciències 2012 Memòria presentada per aspirar al Grau de Doctor per Radu‐Adrian Popescu Vist i plau Prof. Clara Viñas Teixidor Bellaterra, 16 de novembre de 2012 La Professora CLARA VIÑAS i TEIXIDOR, Professora d’Investigació del Consejo Superior de Investigaciones Científicas a l’Institut de Ciència de Materials de Barcelona CERTIFICA Que en RADU‐ADRIAN POPESCU, llicenciat en Enginyeria Química, ha realitzat sota la meva direcció la Tesí Doctoral que porta per títol “Carborane derivatives with electron rich moieties. Synthesis, properties and electronic communication” i que recull aquesta memòria per optar al títol de Doctor en Química per la Universitat Autònoma de Barcelona. I, perquè consti i tingui els efectes corresponents, signa aquest certificat a Bellaterra, a 16 de novembre de 2012. Prof. CLARA VIÑAS i TEIXIDOR ICMAB (CSIC) http://www.icmab.es Campus de la Universitat Autònoma de Barcelona 08193 Bellaterra, Catalunya, Espanya Telf.: +34 935 801 853 Fax.: +34 935 805 729 Aquest treball de recerca ha estat finançat per la Comisión Interministerial de Ciencia y Tecnología, CICYT, mitjançant el projecte CTQ2010-16237 (subprograma BQU) i per la Generalitat de Catalunya amb el projecte 2009/SGR/00279. Alhora, s’ha pogut realitzar gràcies a una beca per la Formació de Personal Universitari (FPU) concedida pel Miniesterio de Ciencia e Innovación, des del juliol del 2008 al juliol del 2012. Aquest treball d’investigació, amb la data de defensa del 18 de gener de 2013 , té com a membres del tribunal a: - Prof. Miquel Solà, Catedràtic de la Universitat de Girona (president). - Dr. Juli Real, Professor Titular d’Universitat de la Universitat Autònoma de Barcelona (secretari). - Prof. Evamarie Hey-Hawkins, Chair of Organometallic Chemistry and Photochemistry at the University of Leipzig, Alemanya (vocal). Com a membres suplents: - Prof. Joan Suades Ortuño, Catedràtic de la Universitat Autònoma de Barcelona. - Dra. Marisa Romero García, Professora Titular de Química de la Universitat de Girona. ACKNOWLEDGEMENTS I’m in debt to many people for the accomplishment of this PhD thesis. The thesis would have been impossible without the unconditional scientific and private support of my PhD director, Prof. Clara Viñas, who put her trust in me and help me the come to Barcelona. I want to thank her for all the knowledge that I recieved from her and for her guidance and dedication. The same debt I owe to Prof. Francesc Teixidor, how contributed to my arrival at ICMAB, and having always the office door open for any consult. His scientific guidance was very valuable to my research, as well the private advices. I would also want to give my gratitude to Dr. José Giner and Dr. Rosario Núñez for their support and advices. To Dr. José Giner I’m also very grateful for his private support. To Prof. Reijo Sillanpää for the University of Jyväskylä (Finland), I wish to thank for the X-ray analysis and the structural characterization. I will like to thank to Dr. Lluis Escriche from Universitat Autònoma de Barcelona for accepting to be my PhD tutor. I am thankful to both Prof. Carles Miravitlles, the former Director of ICMAB, and to Prof. Xavier Obradors, the actual Director of ICMAB for accepting me in the institute and allowing me to use the installations and apparatus. My gratitude for all the administrative and support staff from the ICMAB, without whom, the good working of the institute would be impossible. I wish also to give my thanks to Anna Fernández for all the patience and dedication in doing the NMR and MS analysis and to Jordi Cortés for his dedication to a work that cannot be seen easily, but that makes the laboratories to work perfectly. Also, I thank to Elena Marchante for the electrochemical analysis. I wish to thank to Dr. Pau Farràs and Dr. Emilio Juárez-Pérez for their friendship and the useful discussions about the computational chemistry, and not only. To Dr. Florencia Di Salvo and Dr. Arántzazu González I wish to thank for all that I learned from them and for their friendship and useful advices. My colleagues were an indispensable source of collaboration, friendship and knowledge, and without them, the years of PhD would have been monotones. I’m feeling?? privileged to have seen every day at work, both friends, always available to help on the personal plane, and colleagues, always available to help on the professional plane. Ana C., Albert and Ari know best the moments when they were vital, and I’m forever indebted to them for this. I wish to thank to David for this friendship, amiability and availability to help in any moment I needed. Màrius Tarrés is the “coloured voice” in our group and together with Victor, José, Mireia and Jordi B. made the atmosphere in the office and in the laboratory more entertaining. To Adnana, Marius Lupu, Ana-Daniela, Ivy, Elena O. and Justo, I wish to thank for their collaboration and good companionship in the laboratory. I wish to remind other persons that I had the pleasure to meet and work with, and from which I surely learned something: Patricia, Mònica, Greg, Yolanda, Bea, Chelo, Paula, Chris, Will, Noe, Yan and Damien. All my gratitude to Dr. Cristi Matei and Dr. Dana Berger from Faculty of Applied Chemistry and Materials Science from Polytechnic University of Bucharest for the good recommendations that I received from them in order to come to Barcelona and for introducing me to Prof. Clara Viñas. I also want to thank to Prof. Ana Maria S. Oancea from Faculty of Applied Chemistry and Materials Science from Polytechnic University of Bucharest for her confidence and for introducing me in the world of research, and for guidance during all the years of University courses. As usually, the family is left at the end, but this doesn’t mean that is the least. I wish to thank them for their love and support, without them everything would have been impossible. To Ana, the words are incapable to describe what I owe to her. ORGANITZACIÓ DEL MANUSCRIT D’acord amb la normativa vigent i prèvia acceptació de la comissió de Doctorat de la Universitat Autònoma de Barcelona, aquesta Memòria es presenta com a recull de publicacions. Els treballs inclosos en aquesta memòria són: Addendum I: Articles publicats i presentats a la Comissió de Doctorat de la Universitat Autònoma de Barcelona al juliol de 2012: 1.‐ “Influential Role of Ethereal Solvent on Organolithium Compounds: The Case of Carboranyllithium”. Adrian‐Radu Popescu, Ana Daniela Musteti, Albert Ferrer‐Ugalde, Clara Viñas, Rosario Núñez, and Francesc Teixidor, Chemistry – A European Journal, 2012, 18, 3174‐3184. 2.‐ “Chelation of a proton by oxidized diphosphines.” Adrian‐Radu Popescu, Isabel Rojo, Francesc Teixidor, Reijo Sillanpää, Mikko M. Hänninen, Clara Viñas, Journal of Organometallic Chemistry, Accepted, DOI: 10.1016/j.jorganchem.2012.06.023. 3. – “Uncommon Coordination Behaviour of P(S) and P(Se) Units when Bonded to Carboranyl Clusters: Experimental and Computational Studies on the Oxidation of Carboranyl Phosphine Ligands.” Adrian‐Radu Popescu, Anna Laromaine, Francesc Teixidor, Reijo Sillanpää, Raikko Kivekäs, Joan Ignasi Llambias, and Clara Viñas. Chemistry – A European Journal, 2011, 17, 4429‐4443. Numbering of the compounds Section 1 (1) (2) (3) (4) (5) (6) (7) Section 2 R = Ph R = Ph R = Ph R = Ph (8) (10) (11) (12) R = Ph (9) R’ = H R’ = Me R’ = Ph R’ = SBz R = iPr R = iPr R = iPr R = Cy (13) (15) (16) (17) R = iPr (14) R’ = H R’ = Me R’ = Ph R’ = Me E = O E = O E = O E = O E = O R = Ph (18) R = Ph (19) R = Ph (20) R = iPr (21) R = iPr (22) R’ = Me R’ = Ph R’ = SBz R’ = Me R’ = Ph E = S E = O E = S E = S E = S R = Ph R = Cy (23) R = Ph (24) R = Ph (25) (26) R = iPr (27) R’ = R’ = Ph R’ = H R’ = Me R’ = H PPh2 E = S E = Se E = Se E = Se E = Se R = iPr (28) R = Ph (29) R = Ph (30) R = Ph (31) R = Ph (32) R’ = i R’ = H R’ = Me R’ = Ph R’ = PPh2 P Pr2 E = E’ = O E = E’ = O (34) (35) R = Ph (38) R = Ph R = iPr E = O E = E’ = S (36) E’ = S (37) R = iPr (39) R = Ph R = Ph R = Ph (40) R = Ph (43) R = iPr (41) R = iPr (44) (42) (45) (46) Section 3 (48) (47) (49) (50) (51) R = R’ = -C6H5 (52) R = R’ = -C6H5 (53) R = R’= -α-C10H7 (54) R=R’= -9-C13H9 (55) R=R’= -9-C14H9 (56) R = R’ = -p-C6H4CH3 (57) R = -p-C6H4CH3 R = -H (58) R =R’= -p-C6H4Cl (59) (60) R’ = -o-C6H4CH3 R’ = -m-C6H4NO2 R = R’ = -2-C4H3NH (61) R = R’ = -2-C8H5NH (62) R = R’ = -3- C8H5NH (63) R = R’ = -3-C12H7NH (64) Section 4 (65) (66) (67) (68) (69) (70) (71) i R = PPh2 (72) R = PPr2 (73) R = PCy2 (74) R = SPPh2 (75) R = SePPh2 (76) R = BCy2 (77) (78) Abbreviations ‐ NMR chemical shift FTIR – Fourier Transform Infrared Spectroscopy d – diamagnetic contribution to the shielding constant p – paramagnetic contribution to the shielding constant IEFPCM ‐ Integral Equation Formalism Polarizable Continuum Model *AB – sigma antibondig orbital for the bond between atom A and atom B HF – Hartree‐Fock Theory ρ ‐ electron density HOMO – Highest Occupied Molecular Orbital 2ρ ‐ Laplacian of the electron density lp – electron lone pair *ABC – tricentre antibonding orbital LUMO – Lowest Unoccupied Molecular Orbital AN – acceptor number Me ‐ methyl aq.
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