2011年
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
DALTON TRANSACTIONS
- ,
- ,
- ,
- 巻
- 40
- 号
- 10
- 開始ページ
- 2348
- 終了ページ
- 2357
- 記述言語
- 英語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1039/c0dt01047b
- 出版者・発行元
- ROYAL SOC CHEMISTRY
Photoinduced decarbonylation of Cp*M(CO)(3)Me (M = Mo and W, Cp* = eta(5)-C5Me5) in the presence of xantsilH(2) [xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)] in pentane gave bis(silyl)hydrido complexes Cp*M(kappa Si-2,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(kappa Si-3,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 C N 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,b via 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.
- リンク情報
- ID情報
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- DOI : 10.1039/c0dt01047b
- ISSN : 1477-9226
- Web of Science ID : WOS:000287665000037