Group 12 metal complexes with inner-salt, bis(N,N-disubstituted amino)carbeniumdithiocarboxylate. Asymmetric stretching vibration of thiocarboxylate and reduction potential as probes for the coordination mode

A series of Group 12 metal complexes with bis(N,N-disubstituted amino)carbeniumdithiocarboxylates (RL) have prepared by the reaction of metal perchlorate with RL in EtOH or CH₂Cl_2, and characterized by the X-ray structural analysis, IR spectrum, and electrochemical measurements. The composition of metal and RL and the coordination mode, such as monodentate, chelate, and bridging or capping, depend on both the central metal ion and the substituent on the diaminocarbenium moiety. The useful criteria for the coordination mode are found to be the wavenumber of the -CS₂ asymmetric stretching vibration in the solid state, and the ligand-based reduction potential in solution.