Sulphido bridged dinuclear quadruple bond cleavage product from the reaction between Re2(μ-O2CCH3)4Cl2 and dithiocarbamate: An experimental and theoretical study

Sodium salts of dimethyldithiocarbamate, diethyldithiocarbamate and pyrrolidinedithiocarbamate react with the quadruply bonded dirhenium(III,III) complex [Re-2(mu-O2CCH3)(4)Cl-2] (1) in ethanol to afford the sulphido bridged dinuclear quadruple-bond cleavage products of the type [Re-2(mu-S)(L-R)(4)(OH2)(2)] (2(L-R)) where L-R represents the dithiocarbamato ligands [L-R = S2CNMe2, 2(L-Me); S2CNEt2, 2(L-Et) and S2CN(CH2)(4) , 2(L-P(yr))]. Complexes 2(L-R) 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(L-Et) 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.

Automated summary

The synthesis of sulphido bridged dinuclear rhenium(III) complexes containing dithiocarbamato ligands is reported in this study, along with the spectral and electrochemical properties. The identity of a complex was confirmed through single-crystal X-ray structure determination. The electronic structure and absorption spectra of the complexes were analyzed using DFT and TD-DFT.