New Applications of Weak Donor Atoms to Coordination, Organometallic and Materials Chemistry

Abstract

Abstract Non-aqueous solvated transition metal cations are enjoying renewed popularity as precursors for new applications in molecular and materials chemistry. In two related projects, we are engaged in a general investigation of the syntheses, structures and reactivity of new compounds containing nitrile and ether ligands. A major effort is underway to synthesize homoleptic metal-metal bonded acetonitrile cations of second and third row metals for use in coordination and organometallic chemistry, photochemistry and materials chemistry. Dinuclear carboxylate, halide and halide-phosphine complexes are used to synthesize the metal-metal bonded acetonitrile cations [M2(MeCN)10]4+ (M = Re, Rh). The unusual partially solvated species [Mo2 IV,IV(μ-F)(MeCN)8O2]3+ was prepared from MoCl3(THF)3 in CH3CN. Reactions of the bulky ether-phosphine ligand tris(2,4,6-trimethoxyphenyl)phosphine (TMPP) with the dinuclear cation [Rh2(MeCN)10]4+ and with acetonitrile cations of 3d metals [M(MeCN)6]2+ (M = Co, Ni) produce bis...