Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 13, Issue 10, Pages 2783-2797Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200601425
Keywords
density functional calculations; dithiolenes; S ligands; transition metals; X-ray absorption spectroscopy
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The electronic structures of [M(L-Bu)(2)](-) (L-Bu =3,5-di-tert-butyl-1,2-benzenedithiol; M=Ni, Pd, Pt, Cu, Co, An) complexes and their electrochemically generated oxidized and reduced forms have been investigated by using sulfur K-edge as well as metal K- and L-edge X-ray absorption spectroscopy. The electronic structure content of the sulfur K-edge spectra was determined through detailed comparison of experimental and theoretically calculated spectra. The calculations were based on a new simplified scheme based on quasi-relativistic time-dependent density functional theory (TD-DFT) and proved to be successful in the interpretation of the experimental data. It is shown that dithiolene ligands act as noninnocent ligands that are readily oxidized to the dithiosemiquinonate(-) forms. The extent of electron transfer strongly depends on the effective nuclear charge of the central metal, which in turn is influenced by its formal oxidation state, its position in the periodic table, and scalar relativistic effects for the heavier metals. Thus, the complexes [M(L-Bu)(2)](-) (M=Ni, Pd, Pt) and [Au(L-Bu)(2)] are best described as delocalized class III mixed-valence ligand radicals bound to low-spin d(8) central metal ions while [M(L-Bu)(2)](-) (M=CU, Au) and [M((Bu))(2)](-) (M = Ni, Pd, Pt) contain completely reduced dithiolato(2-) ligands. The case of [Co(L-Bu)(2)](-) remains ambiguous. On the methodological side, the calculation led to the new result that the transition dipole moment integral is noticeably different for S-ls -> valence-pi versus S-ls -> valencea transitions, which is explained on the basis of the differences in radial distortion that accompany chemical bond formation. This is of importance in determining experimental covalencies for complexes with highly covalent metal-sulfur bonds from ligand K-edge absorption spectroscopy.
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