Synthesis, structure and reactivity of platinium and iridium complexes with phosphinodi (benzylsilane) ligands / Cynthia Cuevas-Chávez  

Public ISBD Titre : Synthesis, structure and reactivity of platinium and iridium complexes with phosphinodi (benzylsilane) ligands Type de document : texte imprimé Auteurs : Cynthia Cuevas-Chávez, Auteur ; Sylviane Sabo-Etienne, Directeur de thèse ; Virginia Montiel-Palma, Directeur de thèse Langues : Espagnol (spa) Tags : SILANES  PHOSPHINES  TRANSITION METALS  REACTIVITY  COORDINATION CHEMISTRY Résumé : "The rich chemistry and applicability in such a wide range of fields (e.g. small molecule activation, selective transformations including catalytic developments, etc.) of silicon based pincer-like compounds with transition metals has been witnessed by the remarkable advances in coordination chemistry as well as in organometallics. This is due to the outstanding properties of Si atoms which generate electron rich metal centres concomitantly labilizing trans substituents. However, despite all the plethora of arrangements of such species throughout the literature (e.g. framework, number and nature of anchoring points), metal derivatives with polydentate ligands incorporating two silicon atoms are limited as is the study of their reactivity. Therefore, this thesis presents the synthesis, structure and reactivity of novel Platinum and Iridium complexes supported by the "SiPSi" pincer-type ligand. Interestingly, the square-planar PtII complex of formula trans-[(SiPSi)Pt(PPh3)] (SiPSi = P(o-C6H4CH2SiMe2)2Ph) reversibly reacts with small molecules, H2 and CO, forming the corresponding dihydride and dicarbonyl 18-electron species, respectively. On the other hand, the dimeric complex [Ir(SiPSi)(µ-Cl)]2 dissociates in benzene solution to yield the 14-electron monomeric species [Ir(SiPSi)Cl] which readily reacts with two electron donors. 16- and 18-electron configurations are obtained depending mainly on sterics in the case of P-derivatives. Different dispositions of L ligands on 18-electron species (L = CNCD3, CO) and isomerisation processes were also evidenced. Moreover, even if iridium is prone to perform oxidative additions, we also showed that Si-H agostic bonding can favour C-H activation of an adjacent acidic methylene group leading to a tetradentate ligation." Document : Thèse de Doctorat Etablissement_delivrance : Toulouse 3 en cotutelle avecUniversidad autónoma del estado de Morelos (Cuernavaca, Mexique) Date_soutenance : 08/04/2019 Ecole_doctorale : Sciences de la Matière (SdM)(Toulouse) Domaine : Chimie Organométallique et de Coordination En ligne : https://theses.hal.science/tel-02879013 Synthesis, structure and reactivity of platinium and iridium complexes with phosphinodi (benzylsilane) ligands [texte imprimé] / Cynthia Cuevas-Chávez, Auteur ; Sylviane Sabo-Etienne, Directeur de thèse ; Virginia Montiel-Palma, Directeur de thèse . - [s.d.]. Langues : Espagnol (spa) Tags : SILANES  PHOSPHINES  TRANSITION METALS  REACTIVITY  COORDINATION CHEMISTRY Résumé : "The rich chemistry and applicability in such a wide range of fields (e.g. small molecule activation, selective transformations including catalytic developments, etc.) of silicon based pincer-like compounds with transition metals has been witnessed by the remarkable advances in coordination chemistry as well as in organometallics. This is due to the outstanding properties of Si atoms which generate electron rich metal centres concomitantly labilizing trans substituents. However, despite all the plethora of arrangements of such species throughout the literature (e.g. framework, number and nature of anchoring points), metal derivatives with polydentate ligands incorporating two silicon atoms are limited as is the study of their reactivity. Therefore, this thesis presents the synthesis, structure and reactivity of novel Platinum and Iridium complexes supported by the "SiPSi" pincer-type ligand. Interestingly, the square-planar PtII complex of formula trans-[(SiPSi)Pt(PPh3)] (SiPSi = P(o-C6H4CH2SiMe2)2Ph) reversibly reacts with small molecules, H2 and CO, forming the corresponding dihydride and dicarbonyl 18-electron species, respectively. On the other hand, the dimeric complex [Ir(SiPSi)(µ-Cl)]2 dissociates in benzene solution to yield the 14-electron monomeric species [Ir(SiPSi)Cl] which readily reacts with two electron donors. 16- and 18-electron configurations are obtained depending mainly on sterics in the case of P-derivatives. Different dispositions of L ligands on 18-electron species (L = CNCD3, CO) and isomerisation processes were also evidenced. Moreover, even if iridium is prone to perform oxidative additions, we also showed that Si-H agostic bonding can favour C-H activation of an adjacent acidic methylene group leading to a tetradentate ligation." Document : Thèse de Doctorat Etablissement_delivrance : Toulouse 3 en cotutelle avecUniversidad autónoma del estado de Morelos (Cuernavaca, Mexique) Date_soutenance : 08/04/2019 Ecole_doctorale : Sciences de la Matière (SdM)(Toulouse) Domaine : Chimie Organométallique et de Coordination En ligne : https://theses.hal.science/tel-02879013

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