Dynamic Study of Homoleptic Bimetallic Platinum(II) Complexes Bridged by Fluorinated Benzenethiolates

A variable-temperature 19F NMR study of the homoleptic bimetallic anionic complexes X2[Pt2(μ-SC6F5)2(SC6F5)4] (X = K+, 1a; Bu4N+, 1b), X2[Pt2(μ-p-SC6HF4)2(p-SC6HF4)4] (X = K+, 2a; Bu4N+, 2b), and X2[Pt2(μ-p-SC6F4(CF3))2(p-SC6F4(CF3))4] (X = K+, 3a; Bu4N+, 3b) demonstrates the occurrence of dynamic processes that give rise to several stereoisomeric species in solution. Experimental evidence suggests that both inversion of configuration at the sulfur bridging atoms and hindered rotation about the carbon−sulfur bond are involved in generating the observed isomers. The solid-state X-ray diffraction structures of compounds 1b, 2b, and 3b show that all three complexes contain planar [Pt2(μ-S)2] rings with an anti configuration.