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Ligand K-Edge X-ray Absorption Spectroscopy: A Direct Probe of Ligand−Metal Covalency
Abstract
Ligand K-edge X-ray absorption spectroscopy (XAS) is a new experimental probe of the covalency of a metal-ligand bond. The intensity of the ligand pre-edge feature is proportional to the mixing of ligand orbitals into the metal d orbitals. The methodology to determine covalencies in one-electron (hole) and many-electron systems is described and demonstrated for a series of metal tetrachlorides [MCl(4)](n)(-), metal tetrathiolates [M(SR)(4)](n)(-), and dimeric iron-sulfur (Fe-S) clusters [Fe(2)S(2)(SR)(4)](2-). It is then applied to blue Cu proteins, the Cu(A) site, hydrogen bonding in Fe-S clusters, and the delocalization behavior in [2Fe-2S] vs [4Fe-4S] clusters. The covalencies determined in these studies provide important electronic structure insight into function.
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Cites
Iron-sulfur clusters: nature's modular, multipurpose structures
Beinert, H., Holm, R. H., & Münck, E. (1997) · Science · doi:10.1126/science.277.5326.653 · Cited by 1,944
Cited by
Structure, function, and formation of biological iron-sulfur clusters
Johnson, D. C., Dean, D. R., Smith, A. D., & Johnson, M. K. (2005) · Annual Review of Biochemistry · doi:10.1146/annurev.biochem.74.082803.133518 · Cited by 1,438
Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds
Solomon, E. I., Hedman, B., Hodgson, K. O., Dey, A., & Szilagyi, R. K. (2005) · Coordination Chemistry Reviews · doi:10.1016/j.ccr.2004.03.020 · Cited by 377
Self-citationSynthetic Analogues of Cysteinate-Ligated Non-Heme Iron and Non-Corrinoid Cobalt Enzymes
Kovacs, J. A. (2004) · Chemical Reviews · doi:10.1021/cr020619e · Cited by 273
Metadata
- Authors
- Glaser, T., Hedman, B., Hodgson, K. O., & Solomon, E. I.
- Venue
- Accounts of Chemical Research
- Publisher
- American Chemical Society (ACS)
- Published
- 2000-09-23
- Volume
- 33
- Issue
- 12
- Pages
- 859-868
- ISSN
- 0001-4842 (ISSN-L)
- 1520-4898
- OpenAlex
- W2072714349
- Cited by
- 327
- References
- 1
- FWCI
- 9.27
- Type
- journal article
- Language
- en
- Open access
- closed
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- Glaser, T., Hedman, B., Hodgson, K. O., & Solomon, E. I. (2000). Ligand K-Edge X-ray Absorption Spectroscopy: A Direct Probe of Ligand−Metal Covalency. Accounts of Chemical Research. https://doi.org/10.1021/ar990125c
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Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
Semantic Scholar’s data is described in: Kinney, R., et al. (2023). The Semantic Scholar Open Data Platform. arXiv:2301.10140.
