title: Molecular and electronic structures of oxo-bis(benzene-1,2-dithiolato)chromate(V) monoanions. A combined experimental and density functional study.
abstract: Two oxo-bis(benzene-1,2-dithiolato)chromate(V) complexes, namely, [CrO(L(Bu))2]1- and [CrO(L(Me))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. H2L(Bu) represents the pro-ligand 3,5-di-tert-butylbenzene-1,2-dithiol, and H2L(Me) 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(3d(x2-y2)) pi-donation in Cs geometry providing additional stability to the complexes.
authors.affiliation: Max-Planck Institut für Bioanorganische Chemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
authors.forename: Ruta
authors.initials: R
authors.lastname: Kapre
authors.forename: Kallol
authors.initials: K
authors.lastname: Ray
authors.forename: Isabelle
authors.initials: I
authors.lastname: Sylvestre
authors.forename: Thomas
authors.initials: T
authors.lastname: Weyhermüller
authors.forename: Serena
authors.initials: S
authors.lastname: DeBeer George
authors.forename: Frank
authors.initials: F
authors.lastname: Neese
authors.forename: Karl
authors.initials: K
authors.lastname: Wieghardt
mesh_terms: D000838:Anions; D001555:Benzene Derivatives; D002840:Chromates / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D004583:Electrons; D008280:Magnetics; D015394:Molecular Structure; D013057:Spectrum Analysis; D013696:Temperature; D014050:Toluene / Q000031:analogs & derivatives
chemical_list: D000838:Anions; D001555:Benzene Derivatives; D002840:Chromates; D014050:Toluene; C004848:dithiol