Spectroscopic, and electrochemical studies of [MCl2(η2-N,N-dpksc)] (M = Zn, Cd, Hg and dpksc = di-2-pyridylketone semicarbazone)

Abstract

A series of group 12 metal chlorides of dpksc of the type [MCl2(η2-N,N-dpksc)] (M=Zn, Cd and Hg) were synthesized from the reactions between MCl2 and dpksc in refluxing CH3CN. Spectroscopic measurements performed on protophilic solutions of [MCl2(η2-N,N-dpksc)] divulged sensitivity of [MCl2(η2-N,N-dpksc)] to changes in their surroundings. Variable temperature 1H NMR studies revealed the amine protons to be more sensitive to temperature variations compared to the amide and aromatic protons. Electronic absorption spectral measurements disclosed acid–base inter-conversion between [MCl2(η2-N,N-dpksc)] and its conjugate base [MCl2(η2-N,N-dpksc-H)]−. In dmf, the acidity of [MCl2(η2-N,N-dpksc)] increases in the following order: [ZnCl2(η2-N,N-dpksc)]>[CdCl2(η2-N,N-dpksc)]>[HgCl2(η2-N,N-dpksc)]. The electrochemical properties of [MCl2(η2-N,N-dpksc)] are dominated by a series of irreversible redox transformations pointing to electrochemical decomposition of [MCl2(η2-N,N-dpksc)] upon electronic transfers.