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Metal-free synthesis and characterization of functionalized polyaminoboranes Carlos Antônio de Albuquerque Pinheiro To cite this version: Carlos Antônio de Albuquerque Pinheiro. Metal-free synthesis and characterization of functionalized polyaminoboranes. Polymers. Université Rennes 1, 2017. English. NNT : 2017REN1S092. tel- 01743830 HAL Id: tel-01743830 https://tel.archives-ouvertes.fr/tel-01743830 Submitted on 26 Mar 2018 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. ANNÉE 2017 THÈSE / UNIVERSITÉ DE RENNES 1 sous le sceau de l’Université Bretagne Loire pour le grade de DOCTEUR DE L’UNIVERSITÉ DE RENNES 1 Mention : Chimie Ecole doctorale 3M Matière, Molécules et Matériaux Carlos Antônio de Albuquerque Pinheiro Préparée à l’unité de recherche UMR-CNRS 6226 Institut des Sciences Chimiques de Rennes UFR Sciences et Propriétés de la Matière Thèse soutenue à l'Université de Metal-free synthesis Rennes 1 and characterization le 20 octobre 2017 devant le jury composé de : of functionalized Ghenwa Bouhadir Maître de conférences, Université de Toulouse 3 polyaminoboranes Rapporteure Umit Demirci Professeur, Université de Montpellier Rapporteur Loïc Le Pluart Professeur, Université de Caen Examinateur Sophie Guillaume Directrice de Recherches, Université de Rennes 1 Examinatrice Gilles Alcaraz Directeur de Recherches, Université de Rennes 1 Directeur de thèse Metal-free synthesis and characterization of functionalized polyaminoboranes Carlos Antônio de Albuquerque Pinheiro Empty your mind, be formless, shapeless — like water. Now you put water in a cup, it becomes the cup; You put water into a bottle it becomes the bottle; You put it in a teapot it becomes the teapot. Now water can flow or it can crash. Be water, my friend. Bruce Lee, 2000 Acknowledgment Desde pequeno, sempre quis viajar e conhecer os lugares mencionados nos livros que lia. A oportunidade de fazer um doutorado na França me permitiu conciliar um sonho de infância com meu desenvolvimento acadêmico. Hoje, me sinto realizado tanto pessoalmente quanto profissionalmente. Muitas pessoas foram imprescindíveis para concluir essa etapa de minha vida com sucesso. Antes de mais nada, gostaria de agradecer a minha família, que sempre me apoiou, nunca desacreditando do meu potencial, em especial minha mãe Selma, meu irmão do coração Eduardo e minhas tias Celi e Stella. Me gustaría también agradecer a mi novia Patricia, por su cariño, amor y paciencia, incluso los momentos de mucho estrés en el fin de la tesis. Gracias mi amor. I’d also like to thank my friends, made during the first period in Toulouse, specially Marion and Roberto, for the several hours talking about science and/or nothing, around some coffee and/or beer. Je souhaite aussi remercier mes amis de la deuxième époque que si passait à Rennes, surtout Lucas, Anabella, Eleonora, Cyril, Rachid, Camila et tous les autres membres du bâtiment 10 C, sans lesquelles le séjour dans la Bretagne serait impossible. Um grande abraço para minha família gaúcha, Lili, Betão e Pepê, que me acolheu pela terceira vez com a casa e o coração abertos, transformando uma simples época de trabalho em um período de felicidade e aprendizado. Un grand merci à Gilles, qui m’a accepté comment thésard et m’a guidé par les moments les plus ténèbres comme un ange et par les moments des faiblesses avec force, ce que m’a permis de passer au-delà de mes limites. Um grande obrigado a Katia, que também me acompanha desde o mestrado de maneira tão carinhosa que as vezes a vejo como tia ao invés de professora. Thanks to the O group and the other members of the LCC in Toulouse, with whom we shared good moments and helped me so much to adapt to the new country. Thank you also members of the OMC group in Rennes, very important to me in the final period of this journey. Je souhaite remercier tous les membres du jury qui ont accepté de participer à ma soutenance de thèse et de juger mon travail. Merci à Umit Demirci et à Ghenwa Bouhadir pour fournir une excellente discussion et proportionner une vue plus approfondie de mon sujet de thèse. Merci à Loic Le Pluart et Sophie Guillaume pour enrichir la discussion avec votre expertise. Je remercie encore à Gilles Alcaraz, sans toi, je serai encore en train de rédiger. Table of contents List of compounds .................................................................................................... xii Introduction to inorganic polymers .................................................................... 3 I.1 Carbon-based polymers ................................................................................ 3 I.2 p-block-containing inorganic polymers ...................................................... 6 I.2.1 Group XIV-containing inorganic polymers ........................................... 7 I.2.2 Group XV-containing inorganic polymers .......................................... 23 I.2.3 Group XVI-containing polymers ........................................................... 30 I.3 Boron-based polymers ................................................................................ 32 I.3.1 Boron-Carbon hybrid polymers ............................................................ 33 I.3.2 Boron-Oxygen hybrid polymers ........................................................... 34 I.3.3 Boron-Nitrogen hybrid and inorganic polymers ................................ 35 I.4 Project presentation ..................................................................................... 43 Dehydrocoupling versus boron transfer reaction ........................................... 47 II.1 Reactivity of diisopropylamine-borane and diethylamine in the presence of the [RuH2(η2-H2)2(PCy3)2] ....................................................... 52 II.2 Reactivity of diisopropylaminoborane with amines: insight in the mechanism of the metal-free boron transfer ............................................ 65 II.2.1 Influence of the substitution pattern of the amine. ........................... 75 II.2.2 Reactions using primary amines .......................................................... 76 II.2.3 Reaction with methylamine .................................................................. 85 II.3 Experimental section ................................................................................... 93 Investigation of the polymerization reaction ................................................ 123 III.1 The role of the temperature .................................................................. 123 ix III.2 Evidence of polymer formation ........................................................... 125 III.3 The role of the substitution pattern ..................................................... 130 III.4 Proof of polymer formation ................................................................. 136 III.5 Mechanistic considerations .................................................................. 137 III.6 Overview of the linear poly(alkylamino)boranes ............................. 140 III.7 Conclusion .............................................................................................. 145 III.8 Experimental section ............................................................................. 147 III.8.2 Poly(methylamino)borane ................................................................ 151 III.8.3 Poly(ethylamino)borane .................................................................... 158 III.8.4 Poly(propylamino)borane ................................................................. 168 III.8.5 Poly(butylamino)borane ................................................................... 173 III.8.6 Poly[(ethylamino)borane-ran-(propylamino)borane] (1:1) .......... 178 III.8.7 Poly[(ethylamino)borane-ran-(propylamino)borane] (1:2) .......... 182 III.8.8 Poly[(ethylamino)borane-ran-(butylamino)borane] (1:1) ............. 185 III.8.9 Poly[(ethylamino)borane-ran-(butylamino)borane] (1:2) ............. 190 Enhancing the substitution pattern ................................................................ 197 IV.1 Formation of poly(alkylamino)boranes bearing unsaturated carbon side chains ............................................................................................... 197 IV.2 Formation of silicon-containing polyaminoboranes ......................... 205 IV.3 Post-polymerization functionalization approaches .......................... 206 IV.4 Perspectives ............................................................................................ 209 IV.5 Conclusion .............................................................................................. 209 IV.6 Experimental section ............................................................................. 211 x IV.6.1 Poly(trimethylsilylmethylamino)borane ......................................... 211 IV.6.2 Poly(dimethylethoxysilylpropylamino)borane .............................. 213 IV.6.3 Poly(methyldiethoxysilylpropylamino)borane .............................. 215 IV.6.4 Poly(triethoxysilylpropylamino)borane .........................................
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