Abstract
The square-planar metal dithiolene complexes of o-xylenediyldithioethylene-1,2-dithiolate (oxddt) ligand, (Et4P)[Ni(oxddt)2] (1), (Ph4P)[Ni(oxddt)2] (2) and (Ph4P)[Au(oxddt)2] (3), were prepared and characterized. Among them, the Ni complexes 1 and 2 showed cis-anti-form structures, whose two benzene rings of the Ni(oxddt)2 molecule are closely located to the dithiolene rings but located on the opposite side with respect to the dithiolene ring. In contrast to these Ni complexes, the Au complex 3 has a trans-anti form, suggesting that a Ni/Au substitution in the [M(oxddt)2] modifies those molecular structures in the crystals. An intramolecular π orbital overlap at the α-LUMO+5 level between benzene and dithiolene rings was observed in the [Ni(oxddt)2] complex with the cis-anti-form. Redox behavior of 1 and 3 were investigated by cyclic voltammetry measurements.
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