Pulsed EPR Investigations of Systems Modeling Molybdenum Enzymes:  Hyperfine 
and Quadrupole Parameters of Oxo-17O in [Mo17O(SPh)4]-

Astashkin, Andrei V.; Neese, Frank; Raitsimring, Arnold M.; Cooney, Jon A.; Bultman, Eric; Enemark, John H.

doi:10.1021/ja055472y

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Pulsed EPR Investigations of Systems Modeling Molybdenum Enzymes: Hyperfine and Quadrupole Parameters of Oxo-¹⁷O in [Mo¹⁷O(SPh)₄]^-

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Neese, Frank
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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引用

Astashkin, A. V., Neese, F., Raitsimring, A. M., Cooney, J. A., Bultman, E., & Enemark, J. H. (2005). Pulsed EPR Investigations of Systems Modeling Molybdenum Enzymes: Hyperfine and Quadrupole Parameters of Oxo-¹⁷O in [Mo¹⁷O(SPh)₄]^-. Journal of the American Chemical Society, 127(47), 16713-16722. doi:10.1021/ja055472y.

引用: https://hdl.handle.net/21.11116/0000-0008-36B3-1

要旨

K_a band ESEEM spectroscopy was used to determine the hyperfine (hfi) and nuclear quadrupole (nqi) interaction parameters for the oxo-¹⁷O ligand in [Mo¹⁷O(SPh)₄]^-, a spectroscopic model of the oxo-Mo(V) centers of enzymes. The isotropic hfi constant of 6.5 MHz found for the oxo-¹⁷O is much smaller than the values of ∼20−40 MHz typical for the ¹⁷O nucleus of an equatorial OH₍₂₎ ligand in molybdenum enzymes. The ¹⁷O nqi parameter (e²qQ/h = 1.45 MHz, η ≈ 0) is the first to be obtained for an oxo group in a metal complex. The parameters of the oxo-¹⁷O ligand, as well as other magnetic resonance parameters of [Mo¹⁷O(SPh)₄]^- predicted by quasi-relativistic DFT calculations, were in good agreement with those obtained in experiment. From the electronic structure of the complex revealed by DFT, it follows that the SOMO is almost entirely molybdenum d_xy and sulfur p, while the spin density on the oxo-¹⁷O is negative, determined by spin polarization mechanisms. The results of this work will enable direct experimental identification of the oxo ligand in a variety of chemical and biological systems.