Synthesis and characterisation of hydrido molybdenum and tungsten complexes having a hemilabile tridentate Si,Si,O-ligand: Observation of stepwise hydrosilylation of a nitrile to form an N-silylimine on the metal centre

Takashi Komuro, Rockshana Begum, Rikima Ono, Hiromi Tobita

Research output: Contribution to journalArticlepeer-review

17 Citations (Scopus)

Abstract

Photoinduced decarbonylation of Cp*M(CO) 3 Me (M = Mo and W, Cp* = η 5 -C 5 Me 5 ) in the presence of xantsilH 2 [xantsil = (9,9-dimethylxanthene-4,5-diyl) bis(dimethylsilyl)] in pentane gave bis(silyl)hydrido complexes Cp*M(κ 2 Si,Si-xantsil)(CO) 2 (H) (1a: M = Mo and 1b: M = W) through two-fold Si-H oxidative addition and methane elimination. Further irradiation of 1a,b in toluene afforded tridentate xantsil complexes Cp*M(κ 3 Si,Si,O-xantsil)(CO)(H) (2a: M = Mo and 2b: M = W) via CO dissociation. Reactions of complexes 2a,b with nitriles led to stoichiometric hydrosilylation at the CN triple bond. Thus, reaction of 2a,b with t-BuCN at room temperature afforded N-silyliminoacyl complexes 3a,b, through insertion of a nitrile into the M-Si bond, and the products slowly isomerised to the corresponding N-silylimine complexes 4a,bvia intramolecular hydrogen migration. On the other hand, reaction of 2a,b with PhCN afforded N-silylimine complexes 5a,b directly. The molecular structures of 1a, 3a and 5b were determined by X-ray crystallography, revealing that complex 3a has a 3-centre-2-electron (3c-2e) Mo-Si-H bond.

Original languageEnglish
Pages (from-to)2348-2357
Number of pages10
JournalDalton Transactions
Volume40
Issue number10
DOIs
Publication statusPublished - 2011 Mar 14

ASJC Scopus subject areas

  • Inorganic Chemistry

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