Bis(dimethylphosphino)methane-ligated silver chloride, cyanide and hydride cluster cations: Synthesis and gas-phase unimolecular reactivity

Abstract

Abstract Electrospray ionization mass spectrometry (ESI/MS) of mixtures of AgNO3 or AgBF4 with the capping ligand Me2P(CH2)PMe2 (dmpm, L) in a solution of 1:1 methanol:chloroform or acetonitrile revealed the formation of: dinuclear clusters [Ag2L2]2+, [Ag2(LH)L]+, and [Ag2ClL2]+; trinuclear clusters primarily as [Ag3Cl2L3]+; and the tetranuclear cluster [Ag4Cl3L3]+. Addition of NaBH4 to these solutions of dmpm-protected clusters results in the formation of the silver hydride cluster cations [Ag2HL2]+, [Ag3HL3]2+, [Ag3HL4]2+, [Ag3H(CN)L3]+ and [Ag3HClL3]+ as determined by ESI/MS. Use of NaBD4 confirmed that the borohydride is the source of the hydride in these clusters. The gas-phase unimolec..