Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, Japan.
Dalton Trans. 2011 Mar 14;40(10):2348-57. doi: 10.1039/c0dt01047b. Epub 2010 Dec 6.
Photoinduced decarbonylation of CpM(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 CpM(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 CpM(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 C[triple bond, length as m-dash]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,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.
在戊烷中，CpM(CO)(3)Me（M = Mo 和 W，Cp = η(5)-C(5)Me(5)）在 xantsilH(2) [xantsil = (9,9-二甲基-9H-芴-4,5-二基)双(二甲基硅基)]存在下的光诱导脱羰，通过两次 Si-H 氧化加成和甲烷消除，生成双（硅基）氢化物配合物 CpM(κ(2)Si,Si-xantsil)(CO)(2)(H)（1a：M = Mo 和 1b：M = W）。进一步在甲苯中照射 1a，b 会通过 CO 解离生成三齿配位的 xantsil 配合物 CpM(κ(3)Si,Si,O-xantsil)(CO)(H)（2a：M = Mo 和 2b：M = W）。配合物 2a，b 与腈的反应导致 C[三重键，长度 as m-dash]N 三重键的化学计量的氢硅化。因此，2a，b 与 t-BuCN 在室温下的反应通过腈插入 M-Si 键，生成 N-硅亚胺酰基配合物 3a，b，产物通过分子内氢迁移缓慢异构化为相应的 N-硅亚胺配合物 4a，b。另一方面，2a，b 与 PhCN 的反应直接生成 N-硅亚胺配合物 5a，b。1a、3a 和 5b 的分子结构通过 X 射线晶体学确定，表明配合物 3a 具有 3 中心-2 电子（3c-2e）Mo-Si-H 键。
