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Alkyl and Fluoroalkyl Manganese Pentacarbonyl Complexes As En vue de l'obtention du DOCTORAT DE L'UNIVERSITÉ DE TOULOUSE Délivré par : Institut National Polytechnique de Toulouse (Toulouse INP) Discipline ou spécialité : Chimie Organométallique et de Coordination Présentée et soutenue par : M. ROBERTO MORALES CERRADA le jeudi 15 novembre 2018 Titre : Complexes de manganèse pentacarbonyle alkyle et fluoroalkyle comme modèles d'espèces dormantes de l'OMRP Ecole doctorale : Sciences de la Matière (SDM) Unité de recherche : Laboratoire de Chimie de Coordination (L.C.C.) Directeur(s) de Thèse : MME FLORENCE GAYET M. BRUNO AMEDURI Rapporteurs : M. GERARD JAOUEN, UNIVERSITE PARIS 6 Mme SOPHIE GUILLAUME, CNRS Membre(s) du jury : M. MATHIAS DESTARAC, UNIVERSITE TOULOUSE 3, Président M. BRUNO AMEDURI, CNRS, Membre M. HENRI CRAMAIL, INP BORDEAUX, Membre Mme FLORENCE GAYET, INP TOULOUSE, Membre A mi abuelo Antonio ‐ i ‐ ‐ ii ‐ Remerciements Ce travail a été réalisé dans deux unités de recherche du CNRS : le laboratoire de Chimie de Coordination (LCC) à Toulouse, au sein de l’équipe LAC2, et l’Institut Charles Gerhardt de Montpellier (ICGM), au sein de l’équipe IAM. Il a été codirigé par Dr. Florence Gayet et Dr. Bruno Améduri. Je tiens tout d’abord à remercier Dr. Azzedine Bousseksou, directeur du LCC, et Dr. Patrick Lacroix‐Desmazes, directeur de l’équipe IAM à l’ICGM, pour avoir accepté de m’accueillir au sein de ses laboratoires. Je remercie tout particulièrement mes directeurs de thèse, Dr. Florence Gayet et Dr. Bruno Améduri, pour m’avoir encadré durant ces trois années de doctorat. Un immense merci à tous les deux pour tous leurs conseils, leur patience et leurs connaissances qui m’ont apporté et qui m’ont permis de mener à bien ce travail. Je suis très honoré que Dr. Sophie Guillaume et Prof. Gérald Jaouen aient accepté d’être rapporteurs. Qu’ils trouvent ici l’expression de ma profonde reconnaissance et mes sincères remerciements. J’exprime également ma gratitude au Prof. Mathias Destarac et au Prof. Henri Cramail, qui ont bien voulu être examinateurs. Un très grand merci également au Prof. Rinaldo Poli pour toute son aide apportée pendant ces trois années de thèse et de son expertise en chimie qui m’a permis de résoudre un grand nombre de questions et problèmes auxquels j’ai dû faire face. Qu’il soit aussi remercié pour sa gentillesse, sa disponibilité permanente et pour les nombreux encouragements qu’il m’a prodigués. Je remercie Dr. Vincent Ladmiral et Dr. Christophe Fliedel pour leur aide et leurs conseils, Dr. Antoine Debuigne et Dr. Christophe Detrembleur pour leurs conseils lors des réunions d’avancement du projet, ainsi que l’ensemble de personnes qui ont participé à ce travail. Merci au Dr. Jean‐Claude Daran pour son expertise à déterminer la plupart des structures DRX de ce travail. Mme Dominique Granier et Dr. Arie Van der ‐ iii ‐ Lee pour leur aide en DRX, ainsi que M. Cédric Totée, Prof. Gilles Silly et M. Francis Lacassin pour leur aide et grande expertise en spectroscopie RMN. Dr. Claire Negrell pour son aide en caractérisation des polymères par chromatographie d’exclusion stérique. Je tiens à remercier l’ensemble du personnel du LCC et de l’ICGM, avec une mention spéciale à Sandrine Vincendeau pour toute son aide pour mettre en place un grand nombre d’expériences, ainsi que de m’avoir accueilli au laboratoire toujours avec un grand sourire, Dr. Eric Manoury pour son aide dans le domaine de la chimie organique et sa bonne humeur, Dr. Agnès Labande pour ses conseils et gentillesse et Dr. Abdellatif Manseri pour son support technique et son humour. Je remercie également l’ensemble des personnes que j’ai côtoyé tout au long de la thèse, notamment Dr. Ekaterina Bellan, Maxime Colpaert, Dr. Gérald Lopez, Marc Guerre, Dr. Qizhi Yang, Mohammad Wehbi, Dr. Panagiotis Falireas, Erinque Folgado et Kazuki Komoda. Je remercie l’Agence Nationale de la Recherche (ANR) pour avoir financé ces recherches dans le cadre du projet FLUPOL. Je tiens également à remercier très chaleureusement toute ma famille qui m’a soutenu et motivé pendant ces trois ans. Enfin, je tiens à remercier ma compagne María José pour sa patience et son soutien tout au long de ce travail. ‐ iv ‐ “Once you stop learning, you start dying.” Albert Einstein ‐ v ‐ ‐ vi ‐ Abbreviations list acac Acetylacetonate Acetone‐d6 Deuterated acetone AFCT Addition‐Fragmentation Chain Transfer ATRP Atom Transfer Radical Polymerization b. p. Boiling Point BDE Bond Dissociation Enthalpy Benzene‐d6 Deuterated benzene BrTFE Bromotrifluoroethylene CMRP Cobalt‐Mediated Radical Polymerization CRP Controlled Radical Polymerization CSIRO Commonwealth Scientific and Industrial Research Organization CTA Control Transfer Agent CTFE Chlorotrifluoroethylene D.P. Degree of Polymerization DCM Dichloromethane DFAA Difluoroacetic anhydride DFT Density Functional Theory DMC Dimethyl Carbonate DMF‐d6 Deuterated dimethylformamide DMSO‐d6 Deuterated dimethyl sulfoxide DSC Differential Scanning Calorimetry Ɖ Dispersity FEVE Fluoroethylenevinylether FTIR Fourier‐Transform Infrared spectroscopy HF Hydrogen Fluoride HOAO Highest Occupied Atomic Orbital ITP Iodine Transfer Polymerization ka Activation rate constant kd Deactivation rate constant L Ligand ‐ vii ‐ LUMO Lowest Unoccupied Molecular Orbital MADIX Macromolecular Design by Interchange of Xanthates MAF‐TBE tert-butyl-2-trifluoromethacrylate MMA Methyl Methacrylate Mt Metal NaK Sodium‐potassium metallic liquid alloy NMP Nitroxide‐Mediated Polymerization NMR Nuclear Magnetic Resonance OMRP Organometallic‐Mediated Radical Polymerization Organometallic‐Mediated Radical Polymerization – Degenerative OMRP‐DT Transfer Organometallic‐Mediated Radical Polymerization – Reversible OMRP‐RT Termination ORD Optical Rotatory Dispersion PMA Poly(Methyl acrylate) PMMA Poly(Methyl Methacrylate) ppm Parts‐Per‐Million (10‐6) PPN+ Bis(triphenylphosphine)iminium PS Poly(Styrene) PTFE Poly(Tetrafluoroethylene) PVAc Poly(Vinyl Acetate) PVDF or PVF2 Poly(Vinylidene Fluoride) PVDFH PVDF‐(CF2CH2)‐ PVDFT PVDF‐(CH2CF2)‐ PVF Poly(Vinyl Fluoride) R Alkyl chain RAFT Reversible Addition‐Fragmentation chain Transfer RDRP Reversible‐Deactivation Radical Polymerization RF Fluoroalkyl chain S Styrene SEC Size exclusion chromatography TFAA Trifluoroacetic anhydride TFE Tetrafluoroethylene TFP 3,3,3‐Trifluoropropene TGA Thermogravimetric Analysis ‐ viii ‐ THF Tetrahydrofuran TrFE Trifluoroethylene UV Ultraviolet VDF or VF2 Vinylidene Fluoride VF Vinyl Fluoride ‐ ix ‐ Complexes abbreviations ‐ x ‐ Table of contents General introduction ........................................................................................................ 1 1. State‐of‐the‐art ........................................................................................................... 7 1.1. Fluorinated polymers ........................................................................................... 9 1.1.1. Introduction ............................................................................................... 9 1.1.2. Vinylidene fluoride and poly(vinylidene fluoride) ................................... 10 1.1.3. Polymerization of fluoromonomers ......................................................... 12 1.1.4. Coordination‐insertion polymerization ................................................... 16 1.1.5. Controlled radical polymerization of fluoromonomers ........................... 17 1.2. Metal carbonyl complexes ................................................................................. 25 1.2.1. Structure and bonding ............................................................................. 26 1.2.2. Physical characteristics ............................................................................ 27 1.2.3. Applications .............................................................................................. 28 1.2.4. Techniques of characterization ................................................................ 28 1.2.5. Manganese carbonyl complexes .............................................................. 29 1.2.6. Dimanganese decarbonyl ........................................................................ 29 1.2.7. Manganese carbonyl derivates ................................................................ 32 1.3. Conclusion .......................................................................................................... 37 1.4. References .......................................................................................................... 39 2. Alkylpentacarbonylmanganese(I) complexes .......................................................... 45 2.1. Introduction ........................................................................................................ 47 2.2. Results and discussion ........................................................................................ 49 2.2.1. Synthesis of potassium pentacarbonylmanganate .................................. 49 2.2.2. 1‐Methyl‐2‐methoxy‐2‐oxoethylpentacarbonylmanganese(I), 1 ............ 51 2.2.3. 1‐Acetyloxyethylpentacarbonylmanganese(I), 2 ..................................... 56 2.2.4. 1‐Phenylethylpentacarbonylmanganese(I), 3 .......................................... 63 2.3. Conclusion .......................................................................................................... 68 2.4. Experimental section .......................................................................................... 70 2.5. References .........................................................................................................
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