Probing the Electronic Structures of [Cu_2(í-XR_2)]^(n+) Diamond Cores as a Function of the Bridging X Atom (X = N or P) and Charge (n = 0, 1, 2)
Abstract
A series of dicopper diamond core complexes that can be isolated in three different oxidation states ([Cu_2(μ-XR_2)]^(n+), where n = 0, 1, 2 and X = N or P) is described. Of particular interest is the relative degree of oxidation of the respective copper centers and the bridging XR_2 units, upon successive oxidations. These dicopper complexes feature terminal phosphine and either bridging amido or phosphido donors, and as such their metal−ligand bonds are highly covalent. Cu K-edge, Cu L-edge, and P K-edge spectroscopies, in combination with solid-state X-ray structures and DFT calculations, provides a complementary electronic structure picture for the entire set of complexes that tracks the involvement of a majority of ligand-based redox chemistry. The electronic structure picture that emerges for these inorganic dicopper diamond cores shares similarities with the Cu_2(μ-SR)_2 Cu_A sites of cytochrome c oxidases and nitrous oxide reductases.
Additional Information
© 2008 American Chemical Society. Received September 1, 2007. Publication Date (Web): February 26, 2008. Financial support provided by the DOE (PECASE; J.C.P.); the ONR (N00014-06-1016; R.K.S.); and a NSF Graduate Research Fellowship (N.P.M.). Larry Henling and Dr. Mike Day provided crystallographic assistance. Portions of this research were carried out at the Stanford Synchrotron Radiation Laboratory, a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. The SSRL Structural Molecular Biology Program is supported by the Department of Energy, Office of Biological and Environmental Research, and by the National Institutes of Health, National Center for Research Resources, Biomedical Technology Program.Attached Files
Supplemental Material - ja076537v-file001.cif
Supplemental Material - ja076537v_si.pdf
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Additional details
- Eprint ID
- 47973
- DOI
- 10.1021/ja076537v
- Resolver ID
- CaltechAUTHORS:20140805-113442019
- Department of Energy (DOE) PECASE
- Office of Naval Research (ONR)
- N00014-06-1016
- NSF Graduate Research Fellowship
- Department of Energy (DOE) Office of Biological and Environmental Research
- NIH National Center for Research Resources, Biomedical Technology Program
- Created
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2014-08-05Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field