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.

Download
No fulltext has been uploaded. References only!
Journal Article | Original Article | Published | English

No fulltext has been uploaded

Author
; ; ; ; ; ;
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.
Publishing Year
ISSN
eISSN
PUB-ID

Cite this

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.
This data publication is cited in the following publications:
This publication cites the following data publications:

35 Citations in Europe PMC

Data provided by Europe PubMed Central.

Accessing Ni(III)-thiolate versus Ni(II)-thiyl bonding in a family of Ni-N2S2 synthetic models of NiSOD.
Broering EP, Dillon S, Gale EM, Steiner RA, Telser J, Brunold TC, Harrop TC., Inorg Chem 54(8), 2015
PMID: 25835183
X-ray absorption spectroscopy systematics at the tungsten L-edge.
Jayarathne U, Chandrasekaran P, Greene AF, Mague JT, DeBeer S, Lancaster KM, Sproules S, Donahue JP., Inorg Chem 53(16), 2014
PMID: 25068843
The one-electron reduction of dithiolate and diselenolate ligands.
Bushnell EA, Burns TD, Boyd RJ., Phys Chem Chem Phys 16(22), 2014
PMID: 24763493
Near-infrared pigments based on ion-pair charge transfer salts of dicationic and dianionic metal-dithiolene [M(II) = Pd, Pt] complexes.
Espa D, Pilia L, Marchio L, Mercuri ML, Serpe A, Sessini E, Deplano P., Dalton Trans 42(34), 2013
PMID: 23863989
Synthesis, characterization, spectroscopy, electronic and redox properties of a new nickel dithiolene system.
Basu P, Nigam A, Mogesa B, Denti S, Nemykin V., Inorganica Chim Acta 363(12), 2010
PMID: 21057604
Peculiar electronic and vibrational properties of metal-dithiolenes (Ni, Au) based on 1,2,5-thiadiazole-3,4-dithiolato.
Bruno G, Almeida M, Simao D, Mercuri ML, Pilia L, Serpe A, Deplano P., Dalton Trans (3), 2009
PMID: 19122907

Export

0 Marked Publications

Open Data PUB

Web of Science

View record in Web of Science®

Sources

PMID: 15369373
PubMed | Europe PMC

Search this title in

Google Scholar