DOCSLIB.ORG

Design of a Bifunctional Alkoxy-NHC Ligand for Assembling Tantalum-Rhodium Heterobimetallic Molecular and Silica-Supported Complexes Ravi Srivastava

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Design of a Bifunctional Alkoxy-NHC Ligand for Assembling Tantalum-Rhodium Heterobimetallic Molecular and Silica-Supported Complexes Ravi Srivastava Design of a bifunctional alkoxy-NHC ligand for assembling tantalum-rhodium heterobimetallic molecular and silica-supported complexes Ravi Srivastava To cite this version: Ravi Srivastava. Design of a bifunctional alkoxy-NHC ligand for assembling tantalum-rhodium het- erobimetallic molecular and silica-supported complexes. Other. Université de Lyon; Rheinisch- westfälische technische Hochschule (Aix-la-Chapelle, Allemagne), 2020. English. NNT : 2020LYSE1047. tel-03171489 HAL Id: tel-03171489 https://tel.archives-ouvertes.fr/tel-03171489 Submitted on 17 Mar 2021 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. N°d’ordre NNT : xxx THESE de DOCTORAT DE L’UNIVERSITE DE LYON opérée au sein de l’Université Claude Bernard Lyon 1 Ecole Doctorale de Lyon No ED206 Spécialité de doctorat : Chimie Discipline : Chimie Industrielle Durable Soutenue publiquement le 16/03/2020 par M. Ravi Srivastava Design of a bifunctional alkoxy-NHC ligand for assembling tantalum- rhodium heterobimetallic molecular and silica-supported complexes Jury: Dr. Marine Desage-El Murr Rapportrice CNRS - UMR 7177 Strasbourg Dr. Vincent César Rapporteur CNRS - UPR 8241 Toulouse Prof. Regina Palkovits Examinatrice RWTH Aachen University Dr. Stéphane Bellemin-Laponnaz Examinateur CNRS - UMR 7504 Strasbourg Dr. Nathanaelle Schneider Examinatrice CNRS - UMR 9006 Palaiseau Prof. Abderrahmane Amgoune Examinateur Université Claude Bernard Lyon 1 Prof. Walter Leitner Co-directeur de thèse RWTH Aachen University Dr. Clément Camp Co-encadrant de thèse CNRS - UMR 5265 Lyon Invitée: Dr. Alessandra E. Quadrelli Directrice de thèse CNRS - UMR 5265 Lyon “Design of a bifunctional alkoxy-NHC ligand for assembling tantalum-rhodium heterobimetallic molecular and silica-supported complexes” Der Fakultät für Mathematik, Informatik und Naturwissenschaften der RWTH Aachen University vorgelegte Dissertation zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften von Ravi Srivastava, M. Sc. aus Bhatpurva, Deoria (Uttar Pradesh), Indien UNIVERSITE Claude BERNARD – LYON 1 Président de l’Université M. Frédéric FLEURY Président du Conseil Académique M. Hamda BEN HADID Vice-Président du Conseil d’Administration M. Didier REVEL Vice-Président du Conseil des Etudes et de la Vie M. Philippe CHEVALLIER Universitaire Vice-Président de la Commission de Recherche M. Fabrice VALLEE Directeur Général des Services M. Damien VERHAEGHE COMPOSANTES SANTE Faculté de Médecine Lyon-Est-Claude Bernard Doyen : M. Gilles RODE Faculté de Médecine et Maïeutique Lyon Sud Charles Doyenne : Mme Carole BURILLON Mérieux UFR d’Odontologie Doyenne : Mme Dominique SEUX Institut des Sciences Pharmaceutique et Biologiques Directrice : Mme Christine VINCIGUERRA Institut des Sciences Techniques de la Réadaptation Directeur : M. Xavier PERROT Département de Formation et Centre de Recherche Directrice : Mme Anne-Marie en Biologie Humaine SCHOTT COMPOSANTES & DEPARTMENTS DE SCIENCES & TECHNOLOGIE UFR Biosciences Directrice : Mme Kathrin GIESELER Département Génie Electrique et des Procédés (GEP) Directrice : Mme Rosaria FERRIGNO Département Informatique Directeur : M. Behzad SHARIAT Département Mécanique Directeur : M. Marc BUFFAT UFR - Faculté des Sciences Administrateur Provisoire : M. Bruno ANDRIOLETTI UFR (STAPS) Directeur : M. Yannick VANPOULLE Observatoire de Lyon Directeur : Mme Isabelle DANIEL Ecole Polytechnique Universitaire Lyon 1 Directeur : Emmanuel PERRIN Ecole Supérieure de Chimie, Physique, Electronique Directeur : Bernard BIGOT (CPE Lyon) Institut Universitaire de Technologie de Lyon 1 Directeur : M. Christophe VITON Institut de Science Financière et d’Assurances Directeur : M. Nicolas LEBOISNE ESPE Administrateur Provisoire : M. Pierre CHAREYRON This doctoral research project was part of Erasmus mundus joint doctoral (EMJD) program offered by Sustainable Industrial Chemistry (SINCHEM) consortium under the aegis of ERASMUS+ action program. The research work was carried out in two different universities. The synthesis and characterisation of the organometallic complexes was carried at “University Claude Bernard Lyon 1” in surface organometallic chemistry team at C2P2, CPE Lyon. The computational calculations for the dinitrogen activation was carried out at “RWTH Aachen University” in Institute of technical and macromolecular chemistry (ITMC). Table of Contents List of Abbreviations………………………………………………………………………………………………………………..i ABSTRACT……………………………………………………………………………………………………………………………….iii RÉSUMÉ…………………………………………………………………………………………………………………………………….v ZUSAMMENFASSUNG…………………………………………………………………………………………………………..vii Summary………………………………………………………………………………………………………………………………….ix Résumé…………………………………………………………………………………………………………………………………xxii Chapter 1. Bibliography……………………………………………………………………………………………………………. 1.1) Introduction………………………………………………………………………………………………………………………….. 1.1.1) An overview of heterobimetallic Early-Late transition metal complexes……………………………1 1.1.2) Surface Organometallic Chemistry (SOMC): An approach to realize well defined surface- supported complexes…………………………………………………………………………………………………………………… 1.1.2.1) Presentation…………………………………………………………………………………………………………………….9 1.1.2.2) Silica-supported heterobimetallic species prepared through SOMC…………………………….15 1.1.2.3) Molecular silanols as homogeneous molecular models of silica……………………………………16 1.2) Objectives of this PhD work: synthesis of silica-supported early-late heterobimetallic complex bridged by a bifunctional N-heterocyclic carbene (NHC)………………………………………….19 References…………………………………………………………………………………………………………………………………… Chapter 2. Synthesis and characterization of bifunctional N-heterocyclic carbene (NHC)…………………………………………………………………………………………………………………………………………. 2.1) Introduction………………………………………………………………………………………………………………………….. 2.1.1) Bifunctional ligands for the assembly of early/late heterobimetallic complexes……………..31 2.1.2) Recent literature on bifunctional NHC……………………………………………………………………………33 2.1.3) Ligand design…………………………………………………………………………………………………………………..37 2.2) Results and Discussion…………………………………………………………………………………………………………. 2.2.1) One pot, fast and scalable Synthesis of a new imidazolium salt and its characterization……………………………………………………………………………………………………………………….39 2.2.2) Synthesis and Characterization of free NHC ligand……………………………………………………….43 Conclusion………………………………………………………………………………………………………………………………..51 References……………………..……………………………………………………………………………………………………………. Experimental section ………………………………………………………………………………………………………………….. Chapter 3. Synthesis and Characterisation of metal-NHC complexes……………………………….. 3.1) Introduction………………………………………………………………………………………………………………………….. 3.1.1) Examples of early-late tantalum-rhodium heterobimetallic complexes and the synthetic… protocols involved therein……………………………………………………………………………………………………….63 3.2) Results and Discussion…………………………………………………………………………………………………………. 3.2.1) Synthesis and Characterization of monometallic tantalum-NHC species………………………….. 3.2.1.1) Synthesis of tantalum-alkylidene NHC complex…………………………………………………………..67 3.2.1.2) Decomposition of tantalum-alkylidene NHC complex at room temperature………………69 3.2.1.3) Synthesis of tantalum imido alkylidene NHC complex…………………………………………………73 3.2.2) Synthesis and characterization of monometallic rhodium-NHC species……………………….75 3.3) Synthesis of Ta-Rh bimetallic complex………………………………………………………………………………… 3.3.1) Insertion of Rh into the tantalum-NHC complex……………………………………………………………86 t t 3.3.2) Reaction between the rhodium-NHC complex and Ta(CH Bu)(CH2 Bu)3………………………92 t t 3.3.3) Synthesis of [Ta(μ-L)(N Bu)(CH2 Bu)2Rh(COD)Cl] by using tantalum imido alkylidene….. t t Ta(μ-L)(N Bu)(CH2 Bu)2 as the tantalum precursor…………………………………………………………………92 Conclusion……………………………………………………………………………………………………………………………….96 References…………………..………………………………………………………………………………………………………………. Experimental section…………………………………………………………………………………………………………………… Chapter 4. Development of POSS based homogeneous molecular model of the bimetallic complex and the synthesis of silica-supported early-late heterobimetallic complexes………………………………………………………………………………………………………………………………….. 4.1) Introduction………………………………………………………………………………………………………………………….. 4.1.1) Recent advances in silica-supported heterobimetallic complexes………………………………….117 4.1.2) Two different routes to synthesize the silica supported bimetallic complexes……………..120 4.2) Results and Discussion…………………………………………………………………………………………………………. 4.2.1) Synthesis and Characterization of POSS based heterobimetallic complex…………………….121 4.2.2) Synthesis, characterization and reactivity of tris(tert-butoxy) silanol heterobimetallic…… derivatives……………………………………………………………………………………………………………………………….126 4.2.3) Surface OrganoMetallic Chemistry (SOMC)……………………………………………………………………. 4.2.3.1) Synthesis and characterization of the silica support: SBA15-700……………………………………132 4.2.3.2) Synthesis and characterisation of silica-supported tantalum-NHC species………………133 4.2.3.3) Preparation and characterization of silica-supported Ta/Rh heterobimetallic species…. .……………………………………………………………………………………………………………………………………………...137
Load more

Recommended publications
  • Preparation and Characterization of Iridium Hydride and Dihydrogen Complexes Relevant to Biomass Deoxygenation
    Preparation and Characterization of Iridium Hydride and Dihydrogen Complexes Relevant to Biomass Deoxygenation Jonathan M. Goldberg A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy University of Washington 2017 Reading Committee: D. Michael Heinekey, Chair Karen I. Goldberg, Chair Brandi M. Cossairt Program Authorized to Offer Degree: Department of Chemistry © Copyright 2017 Jonathan M. Goldberg University of Washington Abstract Preparation and Characterization of Iridium Hydride and Dihydrogen Complexes Relevant to Biomass Deoxygenation Jonathan M. Goldberg Chairs of the Supervisory Committee: Professor D. Michael Heinekey Professor Karen I. Goldberg Department of Chemistry This thesis describes the fundamental organometallic reactivity of iridium pincer complexes and their applications to glycerol deoxygenation catalysis. These investigations provide support for each step of a previously proposed glycerol deoxygenation mechanism. Chapter 1 outlines the motivations for this work, specifically the goal of using biomass as a chemical feedstock over more common petroleum-based sources. A discussion of the importance of transforming glycerol to higher value products, such as 1,3-propanediol, is discussed. Chapter 2 describes investigations into the importance of pincer ligand steric factors on the coordination chemistry of the iridium metal center. Full characterization of a five-coordinate iridium-hydride complex is presented; this species was previously proposed to be a catalyst resting state for glycerol deoxygenation. Chapter 3 investigates hydrogen addition to R4(POCOP)Ir(CO) R4 3 t i R4 R4 3 [ POCOP = κ -C6H3-2,6-(OPR2)2 for R = Bu, Pr] and (PCP)Ir(CO) [ (PCP) = κ -C6H3-2,6- t i (CH2PR2)2 for R = Bu, Pr] to give cis- and/or trans-dihydride complexes.
    [Show full text]
  • Binuclear Copper(I) Borohydride Complex Containing Bridging Bis
    crystals Article Binuclear Copper(I) Borohydride Complex Containing Bridging Bis(diphenylphosphino) Methane Ligands: Polymorphic Structures of 2 [(µ2-dppm)2Cu2(η -BH4)2] Dichloromethane Solvate Natalia V. Belkova 1 ID , Igor E. Golub 1,2 ID , Evgenii I. Gutsul 1, Konstantin A. Lyssenko 1, Alexander S. Peregudov 1, Viktor D. Makhaev 3, Oleg A. Filippov 1 ID , Lina M. Epstein 1, Andrea Rossin 4 ID , Maurizio Peruzzini 4 and Elena S. Shubina 1,* ID 1 A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 119991 Moscow, Russia; [email protected] (N.V.B.); [email protected] (I.E.G.); [email protected] (E.I.G.); [email protected] (K.A.L.); [email protected] (A.S.P.); [email protected] (O.A.F.); [email protected] (L.M.E.) 2 Inorganic Chemistry Department, Peoples’ Friendship University of Russia (RUDN University), 117198 Moscow, Russia 3 Institute of Problems of Chemical Physics, Russian Academy of Sciences (IPCP RAS), 142432 Moscow, Russia; [email protected] 4 Istituto di Chimica dei Composti Organometallici Consiglio Nazionale delle Ricerche (ICCOM CNR), 50019 Sesto Fiorentino, Italy; [email protected] (A.R.); [email protected] (M.P.) * Correspondence: [email protected]; Tel.: +7-495-135-5085 Academic Editor: Sławomir J. Grabowski Received: 18 September 2017; Accepted: 17 October 2017; Published: 20 October 2017 Abstract: Bis(diphenylphosphino)methane copper(I) tetrahydroborate was synthesized by ligands exchange in bis(triphenylphosphine) copper(I) tetrahydroborate, and characterized by XRD, FTIR, NMR spectroscopy. According to XRD the title compound has dimeric structure, [(µ2-dppm)2Cu2(η2-BH4)2], and crystallizes as CH2Cl2 solvate in two polymorphic forms (orthorhombic, 1, and monoclinic, 2) The details of molecular geometry and the crystal-packing pattern in polymorphs were studied.
    [Show full text]
  • Download Download
    Journal of Chemistry, Vol. 47 (6), P. 779 - 785, 2009 The Interaction of BH2NH2 with HNZ (Z: O, S) in the Gas Phase: Theoretical Study of the Blue Shift of N-H...H-B Dihydrogen Bonds and the Red Shift of N-H...O and N-H...S Hydrogen Bonds Received 13 September 2007 Nguyen Tien Trung1, Tran Thanh Hue2 1Faculty of Chemistry, Quy Nhon University 2Faculty of Chemistry, Hanoi National University of Education Abstract Theoretical calculations at the MP2/6-311++G(2d,2p) level were performed to study the origin of the B-H...H-N blue-shifting dihydrogen bonds in the complexes of BH2NH2...HNZ (Z = O, S). The stably optimized cyclic structures of the complexes are displayed in figure 1, with interaction energies as table 1. The blue shift of the N5-H7 bond stretching frequencies is observed in the B9-H4...H7-N5 dihydrogen bonds for BH2NH2...HNO and BH2NH2...HNS, corresponding to contraction of the N5-H7 bonds (except for slight elongation of the N5-H7 bond found in the complex BH2NH2...HNS), increase of stretching frequencies and decrease of infrared intensities respectively. I - Introduction chemical processes was studied [4, 5]. The authors have pointed out that similar processes Very recently, the 1990s, a new type of were observed for biological systems such as interaction named dihydrogen bond was the enzyme hydrogenate in bacteria and algae. detected for metal organic crystal structure [1, To increase the understanding of dihydrogen 2] which was coined to describe an interaction bonds, Thomas et al. [6] carried out an ab-initio of the type X-H...H-E; where X is a typical theoretical study on the dimmer (BH3NH3)2.
    [Show full text]
  • Divisão De Serviços Técnicos
    UNIVERSIDADE FEDERAL DO RIO GRANDE DO NORTE CENTRO DE CIÊNCIAS EXATAS E DA TERRA INSTITUTO DE QUÍMICA PROGRAMA DE PÓS-GRADUAÇÃO EM QUÍMICA Novos protocolos teóricos utilizados nos estudos das ligações hidrogênio-hidrogênio, na estabilidade do tetraedrano, seus derivados e das reações de diels-alder e na quantificação da afinidade de fármacos ____________________________________________Norberto de Kássio Vieira Monteiro Tese de Doutorado Natal/RN, outubro de 2015 Norberto de Kássio Vieira Monteiro NOVOS PROTOCOLOS TEÓRICOS UTILIZADOS NOS ESTUDOS DAS LIGAÇÕES HIDROGÊNIO-HIDROGÊNIO, NA ESTABILIDADE DO TETRAEDRANO, SEUS DERIVADOS E DAS REAÇÕES DE DIELS-ALDER E NA QUANTIFICAÇÃO DA AFINIDADE DE FÁRMACOS. Orientador: Caio Lima Firme NATAL/RN 2015 Divisão de Serviços Técnicos Catalogação da Publicação na Fonte. UFRN Biblioteca Setorial do Instituto de Química Monteiro, Norberto de Kássio Vieira. Novos protocolos teóricos utilizados nos estudos das ligações hidrogênio-hidrogênio, na estabilidade do tetraedrano, seus derivados e das reações de diels-alder e na quantificação da afinidade de fármacos / Norberto de Kássio Vieira Monteiro. – Natal, RN, 2015. 167 f. : il. Orientador: Caio Lima Firme. Tese (Doutorado em Química) - Universidade Federal do Rio Grande do Norte. Centro de Ciências Exatas e da Terra. Programa de Pós-Graduação em Química. 1. Diels-Alder – Tese. 2. Ligação H-H – Tese. 3. Tetraedrano – Tese. 4. CYP17 – Tese I. Firme, Caio Lima. II. Universidade Federal do Rio Grande do Norte. III. Título. RN/UFRN/BSE- Instituto de Química CDU 544.142.4:615 (043.3) AGRADECIMENTOS Às minhas três mães: Marilú, Vitória e Dona Francisca. Sem elas, nem sei o que seria de mim. Ao meu amor, Richele, a qual tenho o privilégio de chamar de esposa, pela ajuda e por me aguentar nos momentos de ansiedade e estresse nos anos que me dediquei ao doutorado.
    [Show full text]
  • WO 2013/185114 A2 12 December 2013 (12.12.2013) P O P C T
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization I International Bureau (10) International Publication Number (43) International Publication Date WO 2013/185114 A2 12 December 2013 (12.12.2013) P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every A61K 38/36 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/US20 13/044842 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KN, KP, KR, 7 June 2013 (07.06.2013) KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, (25) Filing Language: English OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SC, (26) Publication Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 61/657,685 8 June 2012 (08.06.2012) US (84) Designated States (unless otherwise indicated, for every 61/759,817 1 February 20 13 (01.02.2013) US kind of regional protection available): ARIPO (BW, GH, 61/801,603 15 March 2013 (15.03.2013) US GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, 61/829,775 31 May 2013 (3 1.05.2013) US UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, (71) Applicant: BIOGEN IDEC MA INC.
    [Show full text]
  • A Semiempirical Potential Model for H-Terminated Functionalized Surface of Porous Silicon
    Digest Journal of Nanomaterials and Biostructures Vol. 5, No 4, October-December 2010, p. 947-957 A SEMIEMPIRICAL POTENTIAL MODEL FOR H-TERMINATED FUNCTIONALIZED SURFACE OF POROUS SILICON A. IOANID, M. DIEACONU, S. ANTOHE Faculty of Physics, University of Bucharest, Bucharest-Magurele, Romania A semiempirical potential model for functionalized surface of porous silicon has been devised. Considering both the Lennard-Jones and electrostatic contributions for the silicon surface-water and water-water interactions, we have shown that it is probable a Si-H...H-O dihydrogen bond between silicon surface and the interfacial water molecule. Due to their - strong reducing character the (Si3)-H silyl anion behaves as an acceptor of proton. This non-conventional dihydrogen bond between silicon surface and interfacial water is competitive with the classical hydrogen bond of between interfacial water-water molecules so that reduces hydrophobicity of surface. (Received October 1, 2010; accepted October 26, 2010) Keywords: Functionalized surface, porous silicon, dihydrogen bond, silyl anion, hydrophobicity 1. Introduction Porous Silicon (PS) is a redutable biomaterial for devices with potential impact in biological and medical applications concerning detection, transport and interactions of the macromolecules, due to the great ratio surface/volume and to the amphoter (hydrophobic/ hidrophylic) properties of their functionalizated surface. Biocompatibility is the ability of a material to interface by adsorption of a layer of protein, with a biological environment without provoking a defence response. PS can be either a bioactive, a bioinert or a resorbable material, depending on the morphological, chemical and electrical characteristics of the surface layer and those of the biological environment in which it is inserted [1].
    [Show full text]
  • Molecular Modeling in Drug Design
    molecules Molecular Modeling in Drug Design Edited by Rebecca C. Wade and Outi M. H. Salo-Ahen Printed Edition of the Special Issue Published in Molecules www.mdpi.com/journal/molecules Molecular Modeling in Drug Design Molecular Modeling in Drug Design Special Issue Editors Rebecca C. Wade Outi M. H. Salo-Ahen MDPI • Basel • Beijing • Wuhan • Barcelona • Belgrade Special Issue Editors Rebecca C. Wade Outi M. H. Salo-Ahen HITS gGmbH/Heidelberg University Abo˚ Akademi University Germany Finland Editorial Office MDPI St. Alban-Anlage 66 4052 Basel, Switzerland This is a reprint of articles from the Special Issue published online in the open access journal Molecules (ISSN 1420-3049) from 2018 to 2019 (available at: https://www.mdpi.com/journal/molecules/ special issues/MMDD) For citation purposes, cite each article independently as indicated on the article page online and as indicated below: LastName, A.A.; LastName, B.B.; LastName, C.C. Article Title. Journal Name Year, Article Number, Page Range. ISBN 978-3-03897-614-1 (Pbk) ISBN 978-3-03897-615-8 (PDF) c 2019 by the authors. Articles in this book are Open Access and distributed under the Creative Commons Attribution (CC BY) license, which allows users to download, copy and build upon published articles, as long as the author and publisher are properly credited, which ensures maximum dissemination and a wider impact of our publications. The book as a whole is distributed by MDPI under the terms and conditions of the Creative Commons license CC BY-NC-ND. Contents About the Special Issue Editors ..................................... vii Preface to ”Molecular Modeling in Drug Design” ..........................
    [Show full text]
  • Dihydrogen Bonds: a Study
    DIHYDROGEN BONDS: A STUDY David HUGAS GERMÀ ISBN: 978-84-694-2209-0 Dipòsit legal: GI-190-2011 http://hdl.handle.net/10803/7921 This work is licensed under the Creative Commons Attribution-NonCommercial-ShareAlike 3.0 Unported License. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-sa/3.0/ or send a letter to Creative Commons, 171 Second Street, Suite 300, San Francisco, California, 94105, USA. Universitat de Girona Master of Science Thesis Dihydrogen Bonds: A study by David Hugas Germ`a Girona, summer 2010 Doctoral programme of\Qu´ımica te`orica i computacional" Supervisor: Dr. S´ılvia Simon Rabasseda Co-Supervisor: Prof. Dr. Miquel Duran Portas Mem`oria presentada per optar al t´ıtol de Doctor per la Universitat de Girona This work is licensed under the Creative Commons Attribution-NonCommercial-ShareAlike 3.0 Unported License. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-sa/3.0/ or send a letter to Creative Commons, 171 Second Street, Suite 300, San Francisco, California, 94105, USA. Departament de Qu´ımica Institut de Area` de Qu´ımica F´ısica Qu´ımica Computacional La doctora S´ılvia Simon i Rabasseda, professora d'Universitat a l'Area` de Qu´ımica F´ısica de la Universitat de Girona i el professor doctor Miquel Duran i Portas, catedr`atic d'Universitat a l'Area` de Qu´ımica F´ısica de la Universitat de Girona CERTIFIQUEN QUE: En David Hugas i Germ`a, llicenciat en Qu´ımica per la Universitat de Girona, ha realitzat sota la seva direcci´o,a l'Institut de Qu´ımica Com- putacional i al Departament de Qu´ımica de la Facultat de Ci`encies de la Universitat de Girona el treball d'investigaci´oque porta per nom: \Dihydrogen Bonds: A Study" que es presenta en aquesta mem`oria per optar al grau de Doctor per la Universitat de Girona.
    [Show full text]
  • Reactivity of a Ruthenium Bis(Dinitrogen) Complex
    Reactivity of a Ruthenium Bis(Dinitrogen) Complex By Samantha Lau July 2018 Department of Chemistry Imperial College London A thesis submitted for Doctorate of Philosophy Declaration of Originality The work discussed in this thesis was conducted in the Department of Chemistry, Imperial College London, between October 2014 and April 2018. Unless stated otherwise, all the work is entirely my own and has not been submitted for a previous degree at this, or any other university. Copyright Declaration The copyright of this thesis rests with the author and is made available under a Creative Commons Attribution Non-Commercial No Derivatives licence. Researchers are free to copy, distribute or transmit the thesis on the condition that they attribute it, that they do not use it for commercial purposes and that they do not alter, transform or build upon it. For any reuse or redistribution, researchers must make clear to others the licence terms of this work. [1] Abstract This thesis investigated the reactivity of the ruthenium bis(dinitrogen) complex [Ru(H)2(N2)2(PCy3)2] 2 (1), an analogue of the ruthenium bis(dihydrogen) complex [Ru(H)2(η -H2)2(PCy3)2]. It was demonstrated that 1 was able to effect the sp2C–X (X= H, O) bond cleavage of acetophenone substrates to generate 5-membered organometallic intermediates. The by-products from the C–O cleavage reactions were identified as alcohols which also react with 1 at a faster or equal rate to the substrates. The mechanism of these C–X cleavage reactions were probed experimentally and computationally to show that the C–H bond cleavage pathway was operating through a σ-complex assisted metathesis pathway whereas the C–O cleavage pathway was operating through a Ru(II)/Ru(IV) redox mechanism.
    [Show full text]
  • Intermolecular Dihydrogen Bonding in VI, VII, and VIII Group Octahedral Metal Hydride Complexes with Water
    J. Chem. Sci. (2018) 130:98 © Indian Academy of Sciences https://doi.org/10.1007/s12039-018-1498-0 REGULAR ARTICLE Special Issue on Modern Trends in Inorganic Chemistry Intermolecular dihydrogen bonding in VI, VII, and VIII group octahedral metal hydride complexes with water KARAKKADPARAMBIL S SANDHYAb, GEETHA S REMYAa and CHERUMUTTATHU H SURESHa,∗ aChemical Sciences and Technology Division, CSIR-National Institute for Interdisciplinary Science and Technology, Trivandrum, Kerala 695 019, India bGovernment College Kariavattom, Trivandrum, Kerala, India E-mail: [email protected], [email protected] MS received 19 March 2018; revised 23 May 2018; accepted 24 May 2018; published online 12 July 2018 Abstract. The nature of dihydrogen bonding (DHB) in VI, VII, and VIII group octahedral metal hydride complexes with H2O has been studied systematically using quantum theory of atoms-in-molecule (QTAIM) analysis. A dihydrogen bond (H···H) between hydride ligand and hydrogen of H2O is revealed in QTAIM analysis with the identification of a bond critical point (bcp). The DHB is due to the donation of electron density from the hydride ligand to the hydrogen of H2O. A strong linear correlation is observed between intermolecular ρ H···H distance (dHH) and electron density ( ) at the bcp. Structural parameters suggested the highly directional nature of DHB. Weak secondary interactions between oxygen of water and other ligands contribute significantly to the binding energy (Eint) of DHB complex (2.5 to 13.2 kcal/mol). Analysis of QTAIM parameters such as kinetic- (Gc), potential- (Vc) and total electron energy density (Hc) revealed the partially covalent character of DHB in majority of the complexes while a few of them showed closed shell character typical of purely non-covalent interactions.
    [Show full text]
  • NBO Applications, 2008
    NBO 2008 (Jan-Dec) - 910 references Compiled by Emily Wixson; Updated by Ariel Neff 4/16/13 Adalsteinsson, H.; Debusschere, B. J.; Long, K. R.; Najm, H. N. Components for atomistic-to-continuum multiscale modeling of flow in micro- and nanofluidic systems Scientific Programming, (16): 297-313 2008. Adcock, W.; Trout, N. A. Diastereofacial selectivity in some 4-substituted (X) 2-adamantyl derivatives: electronic versus steric effects Journal of Physical Organic Chemistry, (21): 68-72 2008. Agapito, F.; Nunes, P. A.; Costa Cabral, B. J.; Borges dos Santos, R. A.; Martinho Simoes, J. A. Energetic differences between the five- and six-membered ring hydrocarbons: Strain energies in the parent and radical molecules Journal of Organic Chemistry, (73): 6213-6223 2008. Aguilar-Castro, L.; Tlahuextl, M.; Mendoza-Huizar, L. H.; Tapia-Benavides, A. R.; Tlahuext, H. Hydrogen bond studies in substituted N-(2-hydroxyphenyl)-2-[(4- methylbenzenesulfonyl)amino]acetamides Arkivoc: 210-226 2008. Alajarin, M.; Cabrera, J.; Pastor, A.; Sanchez-Andrada, P.; Bautista, D. Polar hetero-Diels-alder reactions of 4-alkenylthiazoles with 1,2,4-triazoline-3,5-diones: An experimental and computational study Journal of Organic Chemistry, (73): 963-973 2008. Albertin, G.; Antoniutti, S.; Baldan, D.; Castro, J.; Garcia-Fontan, S. Preparation of benzyl azide complexes of iridium(III) Inorganic Chemistry, (47): 742-748 2008. Alcoba, D. R.; Ona, O. Determination of energies and electronic densities of functional groups according to partitionings in the physical space Journal of Physical Chemistry A, (112): 10023-10028 2008. Alia, J. D.; Vlaisavljevich, B. Prediction of molecular properties including symmetry from quantum-based molecular structural formulas, VIF Journal of Physical Chemistry A, (112): 9784-9795 2008.
    [Show full text]
  • Analysis of Hydrogen Bonds in Crystals
    crystals Editorial Analysis of Hydrogen Bonds in Crystals Sławomir J. Grabowski 1,2 1 Kimika Fakultatea, Euskal Herriko Unibertsitatea UPV/EHU, and Donostia International Physics Center (DIPC), P.K. 1072, 20080 San Sebastian, Spain; [email protected]; Tel.: +34-943-015477 2 IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain Academic Editor: Helmut Cölfen Received: 12 May 2016; Accepted: 13 May 2016; Published: 17 May 2016 Abstract: The determination of crystal structures provides important information on the geometry of species constituting crystals and on the symmetry relations between them. Additionally, the analysis of crystal structures is so conclusive that it allows us to understand the nature of various interactions. The hydrogen bond interaction plays a crucial role in crystal engineering and, in general, its important role in numerous chemical, physical and bio-chemical processes was the subject of various studies. That is why numerous important findings on the nature of hydrogen bonds concern crystal structures. This special issue presents studies on hydrogen bonds in crystals, and specific compounds and specific H-bonded patterns existing in crystals are analyzed. However, the characteristics of the H-bond interactions are not only analyzed theoretically; this interaction is compared with other ones that steer the arrangement of molecules in crystals, for example halogen, tetrel or pnicogen bonds. More general findings concerning the influence of the hydrogen bond on the physicochemical properties of matter
    [Show full text]