Unusual Coordination Assemblies from Platinum(II) Thienyl and Bithienyl Complexes

Abstract

Dinuclear Pt2Br2(dppf)2(μ-C BH4S2) exchanges with isonicotinic acid to release free bithiophene and gives a molecular square [Pt4(dppf) 4(μ2-O2CC5H4N) 4]4+4OTf- which is an "all-ring" system with four Pt rings disposed at the corners of a larger macrocyclic ring. The related mononuclear complex PtBr(η1(C2)-C4H 3S)(dppf) reacts with AgOTf (OTf = triflate) to give [Pt 2(dppf)2(μ2,η1(C),η 1(S)-C4H3S)2]2+2OTf - with an unusual six-membered ring formed by the fusion of two Pt-thienyl entities at the sulfur sites. All the complexes are structurally characterized by single-crystal X-ray crystallography.