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

Abstract A copper hydride cluster [Cu 8 (μ‐H) 6 (μ‐dppm) 5 ](PF 6 ) 2 (dppm=bis(diphenylphosphino)methane) was prepared from reaction of [CuH(PPh 3 )] 6 with dppm in the presence of [Cu(CH 3 CN) 4 ]PF 6 and exhibited fluxional behaviors in solution where the hydrides and the phosphines are scrambling around the trans ‐bicapped octahedral Cu 8 framework. The Cu 8 H 6 complex showed facile reactivity with CO 2 (1 atm, RT) to afford a tricopper complex, [Cu 3 (μ‐H)(μ‐O 2 CH)(μ‐dppm) 3 ]PF 6 , which could be developed to unprecedented hydrosilylation of CO 2 catalyzed by multinuclear CuH species under mild conditions.