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The structure of a series of [M(bdt)2]q complexes, M = Cu, Ni or Co, bdt = benzene-1,2-dithiolate, q = −1, −2 or −3 with up to two unpaired electrons, has been optimized at B3LYP/6-311G* level of theory as the 6-31G* basis incorrectly produces non-planar metallocycles. Square-planar 1[Cu(bdt)2]−, 2[Ni(bdt)2]− and 3[Co(bdt)2]− systems are the most stable ones in agreement with experimental data. The formal oxidation state of the central atom M defined using the total complex charge q differs from the real M oxidation state based on its d-electron population which is always between M(I) and M(II). The greatest deal of the electron structure changes during the reduction/oxidation is related to the bdt ligands, the strength of their ‘non-innocent’ character depends on M and on the spin state of the complex. These changes are not restricted to sulphur atoms only, including spin density distribution. |
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