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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Abstract
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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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.
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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