Why Is Uranyl Formohydroxamate Red?
Abstract
The complexation of UO22+ by formohydroxamate (FHA–) creates solutions with dark red coloration. The inherent redox activity of formohydroxamate leads to the possibility that these solutions contain U(V) complexes, which are often red. We demonstrate that the reaction of U(VI) with formohydroxamate does not result in reduction, but rather in formation of the putative cis-aquo UO2(FHA)2(H2O)2, whose polymeric solid-state structure, UO2(FHA)2, contains an unusually bent UO22+ unit and a highly distorted coordination environment around a U(VI) cation in general. The bending of the uranyl cation results from unusually strong π donation from the FHA– ligands into the 6d and 5f orbitals of the U(VI) cation. Finally, the alteration of the bonding in the uranyl unit drastically changes its electronic and vibrational features.
- Authors:
-
- Department of Chemistry and Biochemistry, Florida State University, 102 Varsity Way, Tallahassee, Florida 32306, United States
- P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States
- Publication Date:
- Research Org.:
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1179255
- Alternate Identifier(s):
- OSTI ID: 1441134
- Grant/Contract Number:
- FG02-13ER16414; SC0010677; SC0006518
- Resource Type:
- Published Article
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Name: Inorganic Chemistry Journal Volume: 54 Journal Issue: 11; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Silver, Mark A., Dorfner, Walter L., Cary, Samantha K., Cross, Justin N., Lin, Jian, Schelter, Eric J., and Albrecht-Schmitt, Thomas E. Why Is Uranyl Formohydroxamate Red?. United States: N. p., 2015.
Web. doi:10.1021/acs.inorgchem.5b00262.
Silver, Mark A., Dorfner, Walter L., Cary, Samantha K., Cross, Justin N., Lin, Jian, Schelter, Eric J., & Albrecht-Schmitt, Thomas E. Why Is Uranyl Formohydroxamate Red?. United States. https://doi.org/10.1021/acs.inorgchem.5b00262
Silver, Mark A., Dorfner, Walter L., Cary, Samantha K., Cross, Justin N., Lin, Jian, Schelter, Eric J., and Albrecht-Schmitt, Thomas E. Sat .
"Why Is Uranyl Formohydroxamate Red?". United States. https://doi.org/10.1021/acs.inorgchem.5b00262.
@article{osti_1179255,
title = {Why Is Uranyl Formohydroxamate Red?},
author = {Silver, Mark A. and Dorfner, Walter L. and Cary, Samantha K. and Cross, Justin N. and Lin, Jian and Schelter, Eric J. and Albrecht-Schmitt, Thomas E.},
abstractNote = {The complexation of UO22+ by formohydroxamate (FHA–) creates solutions with dark red coloration. The inherent redox activity of formohydroxamate leads to the possibility that these solutions contain U(V) complexes, which are often red. We demonstrate that the reaction of U(VI) with formohydroxamate does not result in reduction, but rather in formation of the putative cis-aquo UO2(FHA)2(H2O)2, whose polymeric solid-state structure, UO2(FHA)2, contains an unusually bent UO22+ unit and a highly distorted coordination environment around a U(VI) cation in general. The bending of the uranyl cation results from unusually strong π donation from the FHA– ligands into the 6d and 5f orbitals of the U(VI) cation. Finally, the alteration of the bonding in the uranyl unit drastically changes its electronic and vibrational features.},
doi = {10.1021/acs.inorgchem.5b00262},
journal = {Inorganic Chemistry},
number = 11,
volume = 54,
place = {United States},
year = {Sat May 09 00:00:00 EDT 2015},
month = {Sat May 09 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/acs.inorgchem.5b00262
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