Dicks, J. P., Zubair, M., Davies, E. S., Garner, C. D., Schulzke, C., Wilson, C. and McMaster, J. (2015) Synthesis, structure and redox properties of asymmetric (cyclopentadienyl)(ene-1,2-dithiolate)cobalt(III) complexes containing phenyl, pyridyl and pyrazinyl units. European Journal of Inorganic Chemistry, 2015(21), pp. 3550-3561. (doi: 10.1002/ejic.201500138)
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Abstract
The compounds [(η5-C5H5)Co{SC(H)CRS}] [R = phenyl (1), pyridin-3-yl (2) or pyrazin-2-yl (3)] have been synthesized and characterized by elemental analysis, 1H NMR, mass spectrometry and X-ray crystallography. The variation in the UV/Vis and redox properties of these compounds alone and upon acidification has been investigated. In CH2Cl2 solution each compound undergoes a reversible one-electron reduction, and the EPR spectrum of each monoanion has been recorded. In the presence of a 5:1 excess of trifluoroacetic acid the one-electron reduction of both 2 and 3 occurs at a less negative potential. The information obtained has been interpreted with the aid of DFT calculations for [1]y, [2]y and [3]y (y = 0 or –1) and the monoprotonated forms [2H]z and [3H]z (z = +1 or 0), and this has provided insight into the nature of the redox-active orbitals in these complexes. The HOMOs and LUMOs of these species are delocalized and each involves contributions from cobalt, ene-1,2-dithiolate and R orbitals. The information from the experimental and theoretical investigations is used to suggest that, for the pyran ring-opened form of the molybdenum cofactor of oxygen-atom-transfer enzymes, the pterin may participate in the redox reactions involved in the catalytic cycle.
Item Type: | Articles |
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Additional Information: | The authors thank the European Research Council (ERC) (projectMocoModels), the Engineering and Physical Sciences ResearchCouncil (EPSRC), the University of Nottingham, UK, TrinityCollege Dublin, Ireland, Ernst-Moritz-Arndt-Universität, Greifs-wald, Germany and the European Union, COST Action CM1003for generously supporting this work. |
Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Wilson, Dr Claire |
Authors: | Dicks, J. P., Zubair, M., Davies, E. S., Garner, C. D., Schulzke, C., Wilson, C., and McMaster, J. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | European Journal of Inorganic Chemistry |
ISSN: | 1434-1948 |
ISSN (Online): | 1099-0682 |
Published Online: | 22 April 2015 |
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