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Title: Why Is Uranyl Formohydroxamate Red?

The complexation of UO 2 2+ 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 UO 2(FHA) 2(H 2O) 2, whose polymeric solid-state structure, UO 2(FHA) 2, contains an unusually bent UO 2 2+ 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:
 [1] ;  [2] ;  [1] ;  [1] ;  [1] ;  [2] ;  [1]
  1. Florida State Univ.,Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
  2. Univ. of Pennsylvania, Philadelphia, PA (United States). P. Roy and Diana T. Vagelos Lab., Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0006518; FG02-13ER16414; SC0010677
Type:
Published Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 11; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1179255
Alternate Identifier(s):
OSTI ID: 1441134

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., 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. doi: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.. 2015. "Why Is Uranyl Formohydroxamate Red?". United States. doi: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 = {2015},
month = {5}
}