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

Article abstract of DOI:10.1002/chem.201702071

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.