Pt···Pt vs Pt···S contacts between Pt-containing heterobimetallic lantern complexes.

A trio of Pt-based heterobimetallic lantern complexes of the form [(py)PtM(SAc)4(py)] (M = Co, 1; Ni, 2; Zn, 3) with unusual octahedral coordination of Pt(II) was prepared from a reaction of [PtM(SAc)4] with excess pyridine. These dipyridine lantern complexes could be converted to monopyridine derivatives with gentle heat to give the series [PtM(SAc)4(py)] (M = Co, 4; Ni, 5; Zn, 6). An additional family of the form [PtM(SAc)4(pyNH2)] (M = Co, 7; Ni, 8; Zn, 9) was synthesized from reaction of [PtM(SAc)4(OH2)] or [PtM(SAc)4] with 4-aminopyridine. Dimethylsulfoxide and N,N-dimethylformamide were also determined to react with [PtM(SAc)4] (M = Co, Ni), respectively, to give [PtCo(SAc)4(DMSO)](DMSO), 10, and [PtNi(SAc)4(DMF)](DMF), 11. Structural and magnetic data for these compounds and those for two other previously published families, [PtM(tba)4(OH2)] and [PtM(SAc)4(L)], L = OH2, pyNO2, are used to divide the structures among three distinct categories based on Pt···Pt and Pt···S distances. In general, the we...