Determination of the metal-dithiolate fold angle in mononuclear molybdenum(V) centers by EPR spectroscopy

Drew, SC and Hanson, GR (2009) Determination of the metal-dithiolate fold angle in mononuclear molybdenum(V) centers by EPR spectroscopy. Inorganic Chemistry, 48 5: 2224-2232. doi:10.1021/ic802343f


Author Drew, SC
Hanson, GR
Title Determination of the metal-dithiolate fold angle in mononuclear molybdenum(V) centers by EPR spectroscopy
Journal name Inorganic Chemistry   Check publisher's open access policy
ISSN 0020-1669
1520-510X
Publication date 2009-03-01
Year available 2009
Sub-type Article (original research)
DOI 10.1021/ic802343f
Open Access Status Not yet assessed
Volume 48
Issue 5
Start page 2224
End page 2232
Total pages 9
Editor Arlene Bristol
Richard Eisenberg
Place of publication United States
Publisher American Chemical Society
Language eng
Subject C1
030606 Structural Chemistry and Spectroscopy
030799 Theoretical and Computational Chemistry not elsewhere classified
030201 Bioinorganic Chemistry
970103 Expanding Knowledge in the Chemical Sciences
970106 Expanding Knowledge in the Biological Sciences
Abstract The active sites of mononuclear molybdenum-containing enzymes contain a low-symmetry MoV−dithiolene intermediate whose structure can be probed using electron paramagnetic resonance (EPR). The relationship between experimental EPR spectra and the electronic and geometric structure of the active site can be difficult to establish, not least because of the low molecular symmetry. When density functional theory is used, it is possible to assess this relationship by systematically varying the geometric structure and comparing the theoretical EPR parameters with those obtained experimentally. We employed this approach to examine the relationship between the metal−dithiolate fold angle and the monoclinic spin Hamiltonian parameters (g, A, β) of a prototypical mononuclear molybdenyl model complex. By comparing the experimental EPR parameters with these results, we show that the metal−dithiolate fold angle of the complex in solution may be obtained from the non-coincidence angle β that transforms the principal axes of g to those of A. This will provide a useful method for probing the structure of the MoV intermediate of mononuclear molybdenum enzymes, where the electronic structure of the active site is modulated by the fold angle of the dithiolate ligand (the “metal−dithiolate folding effect”).
Keyword ELECTRON-PARAMAGNETIC-RESONANCE
Q-Index Code C1
Q-Index Status Confirmed Code

Document type: Journal Article
Sub-type: Article (original research)
Collections: 2010 Higher Education Research Data Collection
Centre for Advanced Imaging Publications
 
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Created: Thu, 03 Sep 2009, 18:35:51 EST by Mr Andrew Martlew on behalf of Centre For Magnetic Resonance