Description of the ground state wave functions of Ni dithiolenes using sulfur K-edge X-ray absorption spectroscopy

Szilagyi RK, Lim BS, Glaser T, Holm RH, Hedman B, Hodgson KO, Solomon EI (2003)
Journal of the American Chemical Society 125(30): 9158-9169.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
The pterin-dithiolene cofactor is an essential component of the catalytic sites of all molybdoenzymes except nitrogenase. Understanding its bonding to transition metals allows for development of electronic structure/function correlations in catalysis. The electronic structure description for a series of bis(dithiolene) complexes ([NiL2](z), L = 1,2-Me2C2S2; Z = 2-, 1 -, 0) using sulfur XAS provides the basis for extension to the biologically relevant metal-containing dithiolenes. The transition dipole integral has been developed for the dithiolene sulfur through correlation of XAS pre-edge energy positions of sulfide-, thiolate-, and enedithiolate-S. The ground state wave functions of all three NiL2 complexes have more than 50% S character experimentally demonstrating the noninnocent behavior of the dithiolene ligand. The S K-edge experimental results are correlated with spin-unrestricted, broken-symmetry density functional calculations. These show only limited spin polarization in the neutral complex and delocalized, ligand based ground states for the mono- and dianionic complexes. These XAS and DFT results are correlated with other spectroscopic features and provide insight into reactivity.
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Zeitschriftentitel
Journal of the American Chemical Society
Band
125
Zeitschriftennummer
30
Seite
9158-9169
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eISSN
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Szilagyi RK, Lim BS, Glaser T, et al. Description of the ground state wave functions of Ni dithiolenes using sulfur K-edge X-ray absorption spectroscopy. Journal of the American Chemical Society. 2003;125(30):9158-9169.
Szilagyi, R. K., Lim, B. S., Glaser, T., Holm, R. H., Hedman, B., Hodgson, K. O., & Solomon, E. I. (2003). Description of the ground state wave functions of Ni dithiolenes using sulfur K-edge X-ray absorption spectroscopy. Journal of the American Chemical Society, 125(30), 9158-9169. doi:10.1021/ja029806k
Szilagyi, R. K., Lim, B. S., Glaser, T., Holm, R. H., Hedman, B., Hodgson, K. O., and Solomon, E. I. (2003). Description of the ground state wave functions of Ni dithiolenes using sulfur K-edge X-ray absorption spectroscopy. Journal of the American Chemical Society 125, 9158-9169.
Szilagyi, R.K., et al., 2003. Description of the ground state wave functions of Ni dithiolenes using sulfur K-edge X-ray absorption spectroscopy. Journal of the American Chemical Society, 125(30), p 9158-9169.
R.K. Szilagyi, et al., “Description of the ground state wave functions of Ni dithiolenes using sulfur K-edge X-ray absorption spectroscopy”, Journal of the American Chemical Society, vol. 125, 2003, pp. 9158-9169.
Szilagyi, R.K., Lim, B.S., Glaser, T., Holm, R.H., Hedman, B., Hodgson, K.O., Solomon, E.I.: Description of the ground state wave functions of Ni dithiolenes using sulfur K-edge X-ray absorption spectroscopy. Journal of the American Chemical Society. 125, 9158-9169 (2003).
Szilagyi, RK, Lim, BS, Glaser, Thorsten, Holm, RH, Hedman, B, Hodgson, KO, and Solomon, EI. “Description of the ground state wave functions of Ni dithiolenes using sulfur K-edge X-ray absorption spectroscopy”. Journal of the American Chemical Society 125.30 (2003): 9158-9169.

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