Metal fragment isomerisation upon grafting a d<sup>2</sup> ML<inf>4</inf> perhydrocarbyl Os complex on a silica surface: Origin and consequence

Romain Berthoud, Nuria Rendón, Frédéric Blanc, Xavier Solans-Monfort, Christophe Copéret, Odile Eisenstein

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Abstract

Grafting of Os bisalkylidene complexes, [Os(CHtBu)2(CH 2tBu)2], on a silica partially dehydroxylated at 700 °C selectively yields an alkylidyne complex [(SiO)Os(CtBu)(CH 2tBu)2] according to mass balance analysis, IR and solid state NMR spectroscopies, but 70% of the silanols remains unreacted. Grafting corresponds to a replacement of one alkyl by a siloxy ligand and induces the isomerisation of the metal fragment from a bis-alkylidene to an alkyl alkylidyne. Molecular (B3PW91) and periodic DFT-calculations show that the bis-alkylidene is the energetically favoured isomer for the perhydrocarbyl complex, while the alkyl alkylidyne isomer is more stable when one of the alkyl ligands is replaced by a siloxy ligand. The change of the nature of the ligand is accompanied with a change of geometry: from a distorted tetrahedral structure for [Os(CHtBu)2(CH2tBu)2] to a butterfly-geometry with apical siloxy and alkylidyne ligands for [(SiO)Os(CtBu)(CH2tBu)2]. Finally, DFT calculations show that grafting occurs via a σ-bond metathesis between the silanol and a metal-alkyl bond and not through the typical addition of the silanol onto the alkylidene ligand. © The Royal Society of Chemistry 2009.
Original languageEnglish
Pages (from-to)5879-5886
JournalDalton Transactions
Issue number30
DOIs
Publication statusPublished - 10 Aug 2009

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