LAUSR

Abstract Sodium salts of dimethyldithiocarbamate, diethyldithiocarbamate and pyrrolidinedithiocarbamate react with the quadruply bonded dirhenium(III,III) complex [Re2(μ-O2CCH3)4Cl2] (1) in ethanol to afford the sulphido bridged dinuclear quadruple-bond cleavage products of the type [Re2(μ-S)(LR)4(OH2)2] (2(LR)) where LR represents the dithiocarbamato ligands [LR = S2CNMe2, 2(LMe); S2CNEt2, 2(LEt) and S2CN(CH2)4, 2(LPyr)]. Complexes 2(LR) are the first example of sulphido bridged dinuclear Re(III) complexes containing the chelating dithiocarbamato ligands. The spectral (IR, UV-vis, NMR) and electrochemical properties of this series of complexes are reported. The identity of 2(LEt) has been established by single-crystal X-ray structure determination. The electronic structure and the absorption spectra of the complexes are scrutinized by the density functional theory (DFT) and time-dependent DFT (TD-DFT) analyses.