Abstract
Two new dithiolate copper(II) and nickel(II) complexes [(Boc-S)2M], where M=Cu (1) and Ni (2) {Boc-SH=tert-butyl N-(2-mercaptoethyl)carbamate} were synthesized and characterized Their methylation reactions with methyl iodide appear to occur intramolecularly at the metal(II)-bound dithiolates, forming the metal(II)-bound dithioether complexes [M(Boc-SCH3)2]I2 with clean second-order constants of 7.95×10−2 and 10.59×10−2M−1s−1, respectively. [Display omitted]
•Two dithiolate complexes were synthesized as models of thiolte alkylating enzymes.•The spectral techniques suggest that both complexes have square planar geometries.•The nickel(II) dithiolte complex may be used as a precursor for nanooxide formation.•The methylation reaction appears to occur intramolecularly at the metal-bound dithiolate.
Two new dithiolate copper(II) and nickel(II) complexes with the ligand tert-butyl N-(2-mercaptoethyl)-carbamate (Boc-SH) were prepared. Their structures were established to be [(Boc-S)2M], where M=Cu (1) and Ni (2) by using elemental analysis, thermal analysis, molar conductivity, FT-IR, Raman, UV/VIS, and ESR as well as EI-mass spectroscopic methods. The X-ray structure of the ligand Boc-SH was also determined. Spectral data showed that the carbamate ligand act as anioinic bidentate through one immine nitrogen and one thiolate sulfur donor atoms. The spectral techniques suggest that both complexes appear to have square planar geometries. The very low electrical conductance of the two complexes supports their neutral nature. The redox behaviors of the obtained complexes were also investigated by cyclic voltammetry. The monomeric nature of both complexes was assessed from their magnetic susceptibility values. The thermoanalytical data evidence that complex (2) is stable up to 165°C and undergo complete decomposition, resulting in NiO as a residual product. The TEM image of the obtained oxide residue showed its nanosize cluster, suggesting that complex (2) may be used as a precursor for the formation of nanooxide. The methylation reactions of the two dithiolate complexes (1) and (2) with methyl iodide appear to occur intramolecularly at the metal(II)-bound dithiolates, forming the metal(II)-bound dithioether complexes [M(Boc-SCH3)2]I2 with clean second-order constants of 7.95×10−2 and 10.59×10−2M−1s−1, respectively.