Coinage metal complexes supported by the tri- and tetraphosphine ligands.

A series of tri- and tetranuclear phosphine complexes of d10 metal ions supported by the polydentate ligands, bis(diphenylphosphinomethyl)phenylphosphine (PPP) and tris(diphenylphosphinomethyl)phosphine (PPPP), were synthesized. All the compounds under study, [AuM2(PPP)2]3+ (M = Au (1), Cu (2), Ag (3)), [M4(PPPP)2]4+ (M = Ag (4), Au (5)), [AuAg3(PPPP)2]4+ (6), and [Au2Cu2(PPPP)2(NCMe)4]4+ (7), were characterized crystallographically. The trinuclear clusters 1–3 contain a linear metal core, while in the isostructural tetranuclear complexes 4–6 the metal framework has a plane star-shaped arrangement. Cluster 7 adopts a structural motif that involves a digold unit bridged by two arms of the PPPP phosphines and decorated two spatially separated CuI ions chelated by the remaining P donors. The NMR spectroscopic investigation in DMSO solution revealed the heterometallic clusters 2, 3, and 6 are stereochemically nonrigid and undergo reversible metal ions redistribution between several species, accompanied by the...