Unexpected reactivities of Cu2(diphosphine)2 complexes in alcohol: Isolation, X-ray crystal structure, and photoluminescent properties of a remarkably stable Cu3(diphosphine) 3(μ3-H)2+ hydride complex

摘要

Treatment of [Cu2(dcpm)2]Y2 (dcpm = bis(dicyclohexylphosphino)methane, Y = ClO4 -, BF4 -, PF6 -, CF3SO3 -) with refluxing MeOH in the presence of KOH afforded hydride complexes [Cu3(dcpm)3(μ3-H)]Y2 (1) in about 85% yield. Refluxing [Cu2(dcpm)2](PF6)2 with MeOH in the presence of NH3·H2O and air gave a carboxylate complex [Cu2(dcpm)2(O2CCH2OH)]PF6 (2) in 40% yield. All of the complexes 1 and 2 have been characterized by X-ray crystallography. The Cu3 cores in 1 are almost perfectly shielded by the dcpm ligands. Intense photoluminescence was observed for 1 both in the solid state and in solution.