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Hydrido complexes of yttrium and lutetium supported by bulky guanidinato ligands [Ln(mu-H){(Me3Si)(2)NC(NCy)(2)}(2)](2) (Ln = Y, Lu): Synthesis, structure, and reactivity

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hal.structure.identifierRussian Acad Sci, GA Razunaev Inst Organomet Chem
dc.contributor.authorLYUBOV, Dmitrii M.
hal.structure.identifierRussian Acad Sci, GA Razunaev Inst Organomet Chem
dc.contributor.authorBUBNOV, Alexey M.
hal.structure.identifierRussian Acad Sci, GA Razunaev Inst Organomet Chem
dc.contributor.authorFUKIN, Georgy K.
hal.structure.identifierA. N. Nesmeyanov Institute of Organoelement Compounds [INEOS]
dc.contributor.authorDOLGUSHIN, Fedor M.
hal.structure.identifierA. N. Nesmeyanov Institute of Organoelement Compounds [INEOS]
dc.contributor.authorANTIPIN, Miklail Yu.
hal.structure.identifierLaboratoire de Chimie des polymères organiques [LCPO]
dc.contributor.authorPELCÉ, Olivier
hal.structure.identifierLaboratoire de Chimie des polymères organiques [LCPO]
dc.contributor.authorSCHAPPACHER, Michèle
hal.structure.identifierInstitut des Sciences Chimiques de Rennes [ISCR]
hal.structure.identifierTeam 1 LCPO : Polymerization Catalyses & Engineering
dc.contributor.authorGUILLAUME, Sophie M.
hal.structure.identifierRussian Acad Sci, GA Razunaev Inst Organomet Chem
dc.contributor.authorTRIFONOV, Alexander A.
dc.date.accessioned2020
dc.date.available2020
dc.date.created2008
dc.date.issued2008
dc.identifier.issn1434-1948
dc.identifier.urihttps://oskar-bordeaux.fr/handle/20.500.12278/20785
dc.description.abstractEnLewis base free hydrido complexes of yttrium and lutetium supported by bulky cyclohexyl- substituted guanidinato ligands, [Ln(mu-H){(Me3Si)(2)NC(NCy)(2)}(2)](2) (Ln = Y, Lu), were synthesized and characterized. Single-crystal X-ray diffraction studies revealed dimeric structures. H-1 NMR spectroscopy shows that complex [Y(mu-H){(Me3Si)(2)NC(NCy)(2)}(2)](2) retains its dimeric structure in C6D6 solution. Scrambling of the hydrido complexes [Ln(mu-H){(Me3Si)(2)NC(NCy)(2)}(2)](2) (Ln = Y, Lu) in C6D6 resulted in an equilibrium mixture containing the heterodimetallic species [{(Me3Si)(2)NC(NCy)(2)}(2)Y(mu-H)(2)-Lu{(Me3Si)(2)NC(NCy)(2)}(2)], indicating the dissociation of dimers and the presence of monomeric species in solution. Both compounds initiate the polymerization of ethylene: the activity of the cyclohexyl- substituted yttrium complex, [Y(mu-H){(Me3Si)(2)NC(NCy)(2)}(2)](2), is much lower than that of the isopropyl-substituted analogue, [Y(mu-H){(Me3Si)(2)NC(NiPr)(2)}(2))(2), while in the case of lutetium the activities of [Ln(mu-H){(Me3Si)(2)NC(NR)(2)}(2)](2) (R = iPr, Cy) are similar. Complexes [Ln(mu-H){(Me3Si)(2)NC(NR)(2)}(2)](2) (Ln = Y, Lu; R = iPr, Cy) were shown to catalyze efficiently the hydrosilylation of 1-nonene with PhSiH3 (at a 1:1 substrates mol ratio) to give the terminal silane PhSiH2(n-C9H19) exclusively. If the hydrosilylation reaction is carried out in the presence of a twofold molar excess of 1-nonene, double addition takes place and leads to the formation of tertiary silane PhSiH(n-C9H19)2, which was obtained in 96% yield. The hydrido complexes [Ln(mu-H){(Me3Si)(2)NC(NiPr)(2)}(2)](2) (Ln = Y, Lu) efficiently initiate the ring-opening polymerization of epsilon-caprolactone to give polymers with molar mass up to 80000. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).
dc.language.isoen
dc.publisherWiley-VCH Verlag
dc.subject.enhydrosilylation
dc.subject.enhydrido complexes
dc.subject.enguanidinato ligands
dc.subject.enpolymerization
dc.subject.enrare earths
dc.subject.enalkyl complexes
dc.title.enHydrido complexes of yttrium and lutetium supported by bulky guanidinato ligands [Ln(mu-H){(Me3Si)(2)NC(NCy)(2)}(2)](2) (Ln = Y, Lu): Synthesis, structure, and reactivity
dc.typeArticle de revue
dc.identifier.doi10.1002/ejic.200701343
dc.subject.halChimie/Polymères
bordeaux.journalEuropean Journal of Inorganic Chemistry
bordeaux.page2090-2098
bordeaux.volume12
bordeaux.hal.laboratoriesLaboratoire de Chimie des Polymères Organiques (LCPO) - UMR 5629*
bordeaux.institutionBordeaux INP
bordeaux.institutionUniversité de Bordeaux
bordeaux.peerReviewedoui
hal.identifierhal-00340056
hal.version1
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00340056v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=European%20Journal%20of%20Inorganic%20Chemistry&rft.date=2008&rft.volume=12&rft.spage=2090-2098&rft.epage=2090-2098&rft.eissn=1434-1948&rft.issn=1434-1948&rft.au=LYUBOV,%20Dmitrii%20M.&BUBNOV,%20Alexey%20M.&FUKIN,%20Georgy%20K.&DOLGUSHIN,%20Fedor%20M.&ANTIPIN,%20Miklail%20Yu.&rft.genre=article


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