4 years ago

A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and its Facile Reaction with CO2

A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and its Facile Reaction with CO2
Bunsho Kure, Kanako Nakamae, Yasuyuki Ura, Takayuki Nakajima, Tomoaki Tanase, Miho Tanaka
A copper hydride cluster [Cu8(μ-H)6(μ-dppm)5](PF6)2 (dppm=bis(diphenylphosphino)methane) was prepared from reaction of [CuH(PPh3)]6 with dppm in the presence of [Cu(CH3CN)4]PF6 and exhibited fluxional behaviors in solution where the hydrides and the phosphines are scrambling around the trans-bicapped octahedral Cu8 framework. The Cu8H6 complex showed facile reactivity with CO2 (1 atm, RT) to afford a tricopper complex, [Cu3(μ-H)(μ-O2CH)(μ-dppm)3]PF6, which could be developed to unprecedented hydrosilylation of CO2 catalyzed by multinuclear CuH species under mild conditions. Copper hydride cluster: An octanuclear complex of [Cu8(μ-H)6(μ-dppm)5](PF6)2 (1), was synthesized by treating [CuH(PPh3)]6 and [Cu(CH3CN)4]PF6 with bis(diphenylphosphino)methane (dppm), and showed interesting scrambling behaviors of the ligands and facile reaction with CO2 to give [Cu3(μ-H)(μ-HCO2)(μ-dppm)3]PF6 (2), which led to catalytic hydrosilylation of CO2 under mild conditions.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201702071

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