Metal centered oxidation or ligand centered oxidation of metal dithiolene? Spectral, electrochemical and structural studies on a nickel-4-pyridine-1,2-dithiolate system

The complex Et4N[Ni(4-pedt)2] (1) (4-pedt = 1-(pyridine-4-yl) ethylene-1,2-dithiolate) was synthesized to investigate the behaviour of metal dithiolene compounds upon protonation and oxidation by absorption spectroscopy, electrochemistry and structural analyses and to further understand the electronic states of the dithiolene compounds. It is unexpected that the 915 nm NIR transition band is not shifted when H+ is added, and it is only affected (blue-shifted) when the compound is oxidized. All the evidence of electronic spectra indicates that the NIR band is relevant to the central [Ni(edt)2] moiety (edt = ethylenedithiolate), not the behaviour of individual Ni ions or ligands. It is also not the band of intermolecular interaction of a dimer. The moderately intense band appearing at 655 nm upon protonation is assigned to the intramolecular charge-transfer band between the [Ni(edt)2] moiety and the pyridine. The redox potentials of the metal dithiolene are sensitive to the protonation of the pyridyl group. The structures of monocationic complex 1 and the protonated compounds [Ni(4-Hpedt)2]·ClO4·H2O (2) and [Ni(4-Hpedt)2]·PhSO3·2DMF (3) were characterized by single crystal X-ray determination. The structural data demonstrate that the oxidation of the monoanionic dithiolene complex to neutral does not change the Ni–S bond distances obviously, which further indicates that the process is not only the metal centered oxidation.