期刊
INORGANIC CHEMISTRY
卷 52, 期 19, 页码 11600-11607出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic401974t
关键词
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资金
- U.S. Department of Energy, Office of Science, Early Career Research Program [DE-SC0006518]
- University of Pennsylvania
- National Science Foundation [OCI-1053575]
- Office of Science (OS), Office of Basic Energy Sciences, of the U.S. Department of Energy (DOE) [DE-AC02-05CH11231]
Electrochemical experiments performed on the complex Ce-IV[2-((BuNO)-Bu-t)py](4), where [2-((BuNO)-Bu-t)py](-) = N-tert-butyl-N-2-pyridylnitroxide, indicate a 2.51 V stabilization of the 4+ oxidation state of Ce compared to [(Bu4N)-Bu-n](2)[Ce(NO3)(6)] in acetonitrile and a 2.95 V stabilization compared to the standard potential for the ion under aqueous conditions. Density functional theory calculations suggest that this preference for the higher oxidation state is a result of the tetrakis(nitroxide) ligand framework at the Ce cation, which allows for effective electron donation into, and partial covalent overlap with, vacant 4f orbitals with delta symmetry. The results speak to the behavior of CeO2 and related solid solutions in oxygen uptake and transport applications, in particular an inherent local character of bonding that stabilizes the 4+ oxidation state. The results indicate a cerium(IV) complex that has been stabilized to an unprecedented degree through tuning of its ligand-field environment.
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