A density functional study of the electronic structure and spin Hamiltonian parameters of mononuclear thiomolybdenyl complexes

Drew, Simon C., Young, Charles G. and Hanson, Graeme R. (2007) A density functional study of the electronic structure and spin Hamiltonian parameters of mononuclear thiomolybdenyl complexes. Inorganic Chemistry, 46 7: 2388-2397. doi:10.1021/ic060586b


Author Drew, Simon C.
Young, Charles G.
Hanson, Graeme R.
Title A density functional study of the electronic structure and spin Hamiltonian parameters of mononuclear thiomolybdenyl complexes
Journal name Inorganic Chemistry   Check publisher's open access policy
ISSN 0020-1669
Publication date 2007
Sub-type Article (original research)
DOI 10.1021/ic060586b
Volume 46
Issue 7
Start page 2388
End page 2397
Total pages 10
Editor Bristol, A.
Eisenberg, R.
Place of publication United States
Publisher American Chemical Society
Collection year 2008
Language eng
Subject 250104 Chemical Spectroscopy
670706 Organic industrial chemicals not elsewhere classified
C1
Abstract The electron paramagnetic resonance spin Hamiltonian parameters of mononuclear thiomolybdenyl complexes based upon the tris(pyrazolyl)borate ligand, together with their molybdenyl analogues, are calculated using density functional theory. The electronic g matrix and Mo-95 hyperfine matrix are calculated as second-order response properties from the coupled-perturbed Kohn-Sham equations. The scalar relativistic zero-order regular approximation (ZORA) is used with an all-electron basis and an accurate mean-field spin-orbit operator which includes all one- and two-electron terms. The principal values and relative orientations of the g and A interaction matrices obtained from the experimental spectra in a previous EPR study are compared with those obtained from unrestricted Kohn-Sham calculations at the BP86 and B3LYP level, and the latter are found to be in good quantitative agreement. A quasi-restricted approach is used to analyze the influence of the various molecular orbitals on g and A. In all complexes the ground state magnetic orbital is d(X)2(-Y)2-based and the orientation of the A matrix is directly related to the orientation of this orbital. The largest single contribution to the orientation of the g matrix arises from the spin-orbit coupling of the d(YZ)-based lowest-unoccupied molecular orbital into the ground state. A number of smaller, cumulative charge-transfer contributions augment the d-d contributions. A comparison of the theoretical EPR parameters obtained using both crystallographic and gas-phase geometry-optimized structures of Tp*MoO(bdt) (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate, bdt = 1,2-benzenedithiolate) suggests a correspondence between the metal-dithiolate fold angle and the angle of noncoincidence between g and A.
Keyword Chemistry, Inorganic & Nuclear
Q-Index Code C1
Q-Index Status Confirmed Code

 
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Created: Thu, 10 Apr 2008, 14:42:01 EST by Lesley-Jayne Jerrard on behalf of Centre For Magnetic Resonance