title: Description of the ground-state covalencies of the bis(dithiolato) transition-metal complexes from X-ray absorption spectroscopy and time-dependent density-functional calculations.
abstract: The electronic structures of [M(L(Bu))(2)](-) (L(Bu)=3,5-di-tert-butyl-1,2-benzenedithiol; M=Ni, Pd, Pt, Cu, Co, Au) 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(L(Bu))(2)](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(1s)-->valence-pi versus S(1s)-->valence-sigma 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.
authors.affiliation: Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr, Germany.
authors.forename: Kallol
authors.initials: K
authors.lastname: Ray
authors.forename: Serena
authors.initials: S
authors.lastname: Debeer George
authors.forename: Edward I
authors.initials: EI
authors.lastname: Solomon
authors.forename: Karl
authors.initials: K
authors.lastname: Wieghardt
authors.forename: Frank
authors.initials: F
authors.lastname: Neese
mesh_terms: D000465:Algorithms; D016227:Benzoquinones / Q000737:chemistry; D002412:Cations; D004563:Electrochemistry; D004579:Electron Transport; D008024:Ligands; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013052:Spectrometry, X-Ray Emission; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry; D013816:Thermodynamics; D013997:Time Factors; D028561:Transition Elements / Q000737:chemistry*; D020002:tert-Butyl Alcohol / Q000031:analogs & derivatives
chemical_list: D016227:Benzoquinones; D002412:Cations; D008024:Ligands; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D028561:Transition Elements; C102217:1,2-benzenedithiol; D013455:Sulfur; D020002:tert-Butyl Alcohol