Synthesis, molecular structure, and voltammetric behaviour of unusually stable cis-dioxobis(diisobutyldithiocarbamato)tungsten(VI)

The unusually stable cis-dioxobis(diisobutyldithiocarbamato)tungsten(VI) [WO2(i-Bu2dtc)2] was synthesized by the reaction between WO4 2− and i-Bu2dtc− in water under the air. The X-ray crystal structure and voltammetric behaviour of the complex are reported. The geometry of the WO2S4 core of the complex is distorted octahedral with two terminal oxo ligands in a cis position to each other. The average WO distance of the complex is 1.719 Å and the bond angle of O–W–O is 104.7°, which are in the range of those of cis-dioxotungsten(VI) complexes. The structural features of [WO2(i-Bu2dtc)2] are very similar to those of corresponding cis-dioxomolybdenum(VI) analogues. The complex [WO2(i-Bu2dtc)2] undergoes one-electron quasi-reversible reduction followed by a homogeneous chemical reaction at more negative potential (−1.40 V vs. SSCE) than the corresponding molybdenum analogue [MoO2(i-Bu2dtc)2] (−0.92 V vs. SSCE) in dichloromethane.