A nickel(II) thiosemicarbazonato complex: synthesis, structure, electrochemistry, and application in catalytic coupling of terminal alkynes with arylboronic acids

Abstract

A simple route for the synthesis of a new square-planar nickel(II) complex of 2-((3-methylthiophen-2-yl)methylene)hydrazinecarbothioamide is described. Elemental analysis, solution conductivity, and spectral measurements were used to authenticate the composition of the complex. In addition, the X-ray crystal structure of the complex was obtained. Each of the two ligands of the centrosymmetric structure is coordinated to the metal center via the azomethine N and the thioimidate S atoms, forming five-membered chelate rings. Infrared and NMR spectroscopic features of the complex are consistent with its molecular structure. The complex displays a quasi-reversible reduction with E 1/2 of −0.83 V (ΔE p 160 mV), indicating that the ligand system can stabilize the Ni(I) oxidation state. The complex acts as an active catalyst for the C–C coupling of aryl acetylenes with arylboronic acids containing a variety of substituents. The influence of solvent, base, reaction temperature, and catalyst loading on the C–C coupling reaction was evaluated. A new square-planar nickel(II) complex bearing 2-((3-methylthiophen-2-yl)methylene)-hydrazinecarbothioamide was synthesized and characterized by elemental analysis, FTIR, NMR, and single-crystal X-ray crystallographic technique. Cyclic voltammetric study indicates stabilization of Ni(I) oxidation state. The complex acts as an effective catalyst for the carbon–carbon cross-coupling reaction of substituted phenylacetylenes with various arylboronic acids under optimized conditions.