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  Molecular and Electronic Structures of Oxo-bis(benzene-1,2-dithiolato)chromate(V) Monoanions. A Combined Experimental and Density Functional Study

Kapre, R., Ray, K., Sylvestre, I., Weyhermüller, T., DeBeer George, S., Neese, F., et al. (2006). Molecular and Electronic Structures of Oxo-bis(benzene-1,2-dithiolato)chromate(V) Monoanions. A Combined Experimental and Density Functional Study. Inorganic Chemistry, 45(9), 3499-3509. doi:10.1021/ic051844s.

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 Creators:
Kapre, Ruta1, Author              
Ray, Kallol1, Author              
Sylvestre, Isabelle1, Author              
Weyhermüller, Thomas1, Author              
DeBeer George, Serena2, Author
Neese, Frank1, Author              
Wieghardt, Karl1, Author              
Affiliations:
1Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              
2Stanford Synchrotron Radiation Laboratory, SLAC, Stanford University, Stanford, California 94309, ou_persistent22              

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 Abstract: Two oxo-bis(benzene-1,2-dithiolato)chromate(V) complexes, namely, [CrO(LBu)2]1- and [CrO(LMe)2]1-, have been synthesized and studied by UV−vis, EPR, magnetic circular dichroism (MCD), and X-ray absorption spectroscopy and by X-ray crystallography; their electro- and magnetochemistries are reported. H2LBu represents the pro-ligand 3,5-di-tert-butylbenzene-1,2-dithiol, and H2LMe is the corresponding 4-methyl-benzene-1,2-dithiol. A structural feature of interest for both the complexes is the folding of the dithiolate ligands about the S−S vector providing Cs symmetry to the complexes. Geometry optimizations using all-electron density functional theory with scalar relativistic corrections at the second-order Douglas−Kroll−Hess (DKH2) and zeroth-order regular approximation (ZORA) levels result in excellent agreement with the experimentally determined structures and electronic and S K-edge X-ray absorption spectra. From DFT calculations, the Cs instead of C2v symmetry for the complexes is attributed to the strong S(3p) → Cr(3dx2-y2) π-donation in Cs geometry providing additional stability to the complexes.

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Language(s): eng - English
 Dates: 2005-10-252006-02-172006-05-01
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ic051844s
 Degree: -

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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 45 (9) Sequence Number: - Start / End Page: 3499 - 3509 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669