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

• Published in: Polyhedron 2021-11, Vol.208, p.115422, Article 115422
• Main Authors: Mallick, Suman, Garu, Purnananda, Chowdhury, Jagannath, Saha, Rajat, Chattopadhyay, Swarup
• Format: Article
• Language: English
• Subjects: Density functional theory; Dirhenium(III); Dithiocarbamates; Quadruple-bond cleavage
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2021.115422

The synthesis and structural characterization of a series of hitherto unreported sulphido bridged dinuclear Re(III) complexes containing the chelating dithiocarbamato ligands from the reaction between Re2(μ-O2CCH3)4Cl2 and dithiocarbamates have been reported. The complexes have similar spectral and electrochemical properties which are consistent with the theoretical study. [Display omitted] 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.