Sulphido bridged dinuclear quadruple bond cleavage product from the reaction between Re2(µ-O2CCH3)4Cl2 and dithiocarbamate: An experimental and theoretical study. (1st November 2021)

• Record Type: Journal Article
• Authors: Mallick, Suman; Garu, Purnananda; Chowdhury, Jagannath; Saha, Rajat; Chattopadhyay, Swarup
• Is Part Of: Polyhedron. Volume 208(2021)
• Publication Date: 2021-11-01
• Subjects: Dirhenium(III) -- Dithiocarbamates -- Quadruple-bond cleavage -- Density functional theory; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2021.115422
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: 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-O2 CCH3 )4 Cl2 and dithiocarbamates have been reported. The complexes have similar spectral and electrochemical properties which are consistent with the theoretical study. Abstract: Sodium salts of dimethyldithiocarbamate, diethyldithiocarbamate and pyrrolidinedithiocarbamate react with the quadruply bonded dirhenium(III, III) complex [Re2 (μ-O2 CCH3 )4 Cl2 ] (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 = S2 CNMe2, 2 (LMe ); S2 CNEt2, 2 (LEt ) and S2 CN(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.