Multisite Reactivity of the Unsaturated Methoxycarbyne Complex [Mo<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>(µ-COMe)(µ-PCy<sub>2</sub>)(µ-CO)]
作者:Daniel García-Vivó、M. Esther García、Miguel A. Ruiz
DOI:10.1021/om701200q
日期:2008.1.1
The methoxycarbyne-bridged complex [Mo2CP2(mu-COMe)(mu-PCy2)(mu-CO)] (1) has a reactive Mo2C center, as illustrated through the addition reactions taking place with [MnCp(CO)(2)(THF)] or gray selenium to give the cluster [MnMo2CP3(mu(3)-COMe)(mu-PCy2)(CO)(4)] and the diselenide complex [Mo2CP2(mu-PCy2)mu-K', eta' :K', eta'-SeC(O)C(OMe)}(mu-K' :K'-Se-2)], respectively. In contrast, the reactions with molecules having active E-H bonds (E = p-block element) involve the cleavage of one of the two C-O bonds in the methoxycarbyne ligand, as observed in the reaction of 1 with HSiPh3 to give the arylcarbyne compound [Mo2Cp2mu-C(2-C6H4SiPh2OMe)}(mu-PCy2)(mu-CO)], this requiring the occurrence of a complex sequence of elemental steps including the cleavage of C-O, C-H, and Si-H bonds, as well as the formation of new C-C and O-Si bonds.