期刊
DALTON TRANSACTIONS
卷 43, 期 43, 页码 16197-16206出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4dt01386g
关键词
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资金
- Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Early Career Research Program of the U.S. Department of Energy [DE-SC006518]
- German Science Foundation [AN 238/16-4]
- University of Pennsylvania
- Research Corporation for Science Advancement (Cottrell Scholar Award)
- NSF [CHE-0840438]
- U.S. National Science Foundation [OCI-1053575]
The trivalent compound K[Ce[N(SiHMe2)(2)](4)] was synthesized and oxidized, providing a convenient route to the reported cerium(IV) compound Ce[N(SiHMe2)(2)](4). Protonolysis reactions of Ce[N(SiHMe2)(2)](4) with tert-butanol, substituted benzyl alcohols, and 2,6-diphenylphenol yielded the neutral tetravalent compounds Ce((OBu)-Bu-t)(4)(py)(2), Ce-2(OCH2C6P5)(8)(thf)(2) (R = Me, F), and Ce(Odpp)(4) (dPP = 2,6-(C6H5)(2)-C6H3). Spectroscopic and electrochemical characterization of the monometallic cerium(IV) silylamide, alkoxide, and aryloxide compounds revealed variable ligand-to-metal charge transfer transitions and metal-based reduction potentials. Computational bonding analyses were performed to complement the physical characterization of the complexes.
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