期刊
INORGANICA CHIMICA ACTA
卷 364, 期 1, 页码 167-171出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2010.07.074
关键词
Non-innocent ligand; Redox; Cyclopentadienyl; Cyclooctatetraenyl; Uranium; Bipyridine
资金
- National Science Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1010002] Funding Source: National Science Foundation
The U4+ cyclooctatetraenyl complex, [(C5Me5)(C8H8)U](2)(mu-C8H8), 1, reacts with two equiv of 4, 4'-dimethyl-2,2'-bipyridine (Me(2)bipy) and 2 equiv of 2,2'-bipyridine (bipy) to form 2 equiv of (eta(5)-C5Me5)(eta(8)-C8H8)U(Me(2)bipy-kappa N-2,N') and (eta(5)-C5Me5)(eta(8)-C8H8)U(bipy-kappa N-2,N'), respectively. X-ray crystallography, infrared spectroscopy, and density functional theory calculations indicate that the products are best described as U4+ complexes of bipyridyl radical anions. Hence, only one of the (C8H8)(2) ligands in 1 acts as a reductant and delivers 2 electrons per equiv of 1. Since the reduction potentials of uncomplexed (C8H8)(2), Me(2)bipy, and bipy are -1.86, -2.15, and -2.10 V vs SCE, respectively, it is likely that prior coordination of the bipyridine reagents enhances the electron transfer. (C) 2010 Elsevier B.V. All rights reserved.
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