Nakamae Kanako, Tanaka Miho, Kure Bunsho, Nakajima Takayuki, Ura Yasuyuki, Tanase Tomoaki
Department of Chemistry, Faculty of Science, Nara Women's University, Kitauoya-nishi-machi, Nara, 630-8506, Japan.
Chemistry. 2017 Jul 18;23(40):9457-9461. doi: 10.1002/chem.201702071. Epub 2017 May 30.
A copper hydride cluster Cu (μ-H) (μ-dppm) (dppm=bis(diphenylphosphino)methane) was prepared from reaction of [CuH(PPh )] with dppm in the presence of [Cu(CH CN) ]PF and exhibited fluxional behaviors in solution where the hydrides and the phosphines are scrambling around the trans-bicapped octahedral Cu framework. The Cu H complex showed facile reactivity with CO (1 atm, RT) to afford a tricopper complex, [Cu (μ-H)(μ-O CH)(μ-dppm) ]PF , which could be developed to unprecedented hydrosilylation of CO catalyzed by multinuclear CuH species under mild conditions.
通过在[Cu(CH₃CN)₄]PF₆存在下，使[CuH(PPh₃)₃]与二苯基膦甲烷（dppm）反应，制备了氢化铜簇合物Cu(μ-H)(μ-dppm)₂（dppm = 双（二苯基膦基）甲烷）。该簇合物在溶液中表现出动态行为，其中氢化物和膦围绕反式双帽八面体铜骨架发生快速交换。Cu-H配合物与CO（1个大气压，室温）反应容易，生成三铜配合物Cu₃(μ-H)(μ-OC(O)CH₃)(μ-dppm)₂，该配合物可用于开发多核CuH物种在温和条件下催化CO的前所未有的硅氢化反应。
