Polymeric and macrocyclic gold(I) complexes with bridging dithiolate and diphosphine ligands

The reaction of digold(I) diphosphine complexes [Au2(O2CCF3)2(μ-Ph2P–X–PPh2)] with dithiols HS–Y–SH can give either macrocyclic complexes [Au2(μ-S–Y–S)(μ-Ph2P–X–PPh2)] or polymeric complexes [Au2(μ-S–Y–S)(μ-Ph2P–X–PPh2)]n. The structures of the macrocyclic complex [Au2{μ-(S-4-C6H4)2S}{μ-Ph2P(CH2)4PPh2}], and the polymeric complexes [Aun{μ-(S–CH2CO2CH2CH2O)2-1,4-C6H4}n(μ-trans-Ph2PCHdouble bond; length as m-dashCHPPh2)n] and [Aun{μ-(S–CH2CO2CH2CH2O)2-1,5-C10H6}n(μ-trans-Ph2PCHdouble bond; length as m-dashCHPPh2)n] have been determined. Evidence is presented that the complexes exist primarily as macrocycles in solution and that, in favorable cases, ring-opening polymerization occurs during crystallization.