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  Description of the Ground‐State Covalencies of the Bis(dithiolato) Transition‐Metal Complexes from X‐ray Absorption Spectroscopy and Time‐Dependent Density‐Functional Calculations

Ray, K., DeBeer George, S., Solomon, E. I., Wieghardt, K., & Neese, F. (2007). Description of the Ground‐State Covalencies of the Bis(dithiolato) Transition‐Metal Complexes from X‐ray Absorption Spectroscopy and Time‐Dependent Density‐Functional Calculations. Chemistry – A European Journal, 13(10), 2783-2797. doi:10.1002/chem.200601425.

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 Creators:
Ray, Kallol1, Author              
DeBeer George, Serena2, Author
Solomon, Edward I.3, Author
Wieghardt, Karl1, Author              
Neese, Frank4, Author              
Affiliations:
1Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              
2Stanford Synchrotron Radiation Laboratory, SLAC, Stanford University, Stanford, CA, 94309, USA, ou_persistent22              
3Department of Chemistry, Stanford University, Stanford, CA 94305, USA, ou_persistent22              
4Lehrstuhl für Theoretische Chemie, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstrasse 12, D-53115 Bonn, Germany, ou_persistent22              

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Free keywords: density functional calculations; dithiolenes; S ligands; transition metals; X-ray absorption spectroscopy
 Abstract: The electronic structures of [M(LBu)2] (LBu=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(LBu)2] (M=Ni, Pd, Pt) and [Au(LBu)2] are best described as delocalized class III mixed‐valence ligand radicals bound to low‐spin d8 central metal ions while [M(LBu)2] (M=Cu, Au) and [M(LBu)2]2− (M=Ni, Pd, Pt) contain completely reduced dithiolato(2−) ligands. The case of [Co(LBu)2] remains ambiguous. On the methodological side, the calculation led to the new result that the transition dipole moment integral is noticeably different for S1s→valence‐π versus S1s→valence‐σ 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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Language(s): eng - English
 Dates: 2006-10-052007-03-162007-03-26
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.200601425
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 13 (10) Sequence Number: - Start / End Page: 2783 - 2797 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058