Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 54, Issue 26, Pages 7534-7538Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201502336
Keywords
cerium; Raman spectroscopy; small-angle X-ray scattering; structure elucidation; X-ray absorption spectroscopy
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Funding
- U.S. DOE, Office of Science, Office of Basic Energy Science, Division of Chemical Sciences, Biosciences and Geosciences [DE-AC02-06CH11357]
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Ceric ammonium nitrate (CAN) is a single-electron-transfer reagent with unparalleled utility in organic synthesis, and has emerged as a vital feedstock in diverse chemical industries. Most applications use CAN in solution where it is assigned a monomeric [Ce-IV(NO3)(6)](2-) structure; an assumption traced to half-century old studies. Using synchrotron X-rays and Raman spectroscopy we challenge this tradition, converging instead on an oxo-bridged dinuclear complex, even in strong nitric acid. Thus, one equivalent of CAN is recast as a two-electron-transfer reagent and a redox-activated superbase, raising questions regarding the origins of its reactivity with organic molecules and giving new fundamental insight into the stability of polynuclear complexes of tetravalent ions.
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