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DFT and CASPT2 analysis of polymetallic uranium nitride and oxide complexes: how theory can help when X-ray analysis is inadequate.

Authors
Type
Published Article
Journal
Journal of the American Chemical Society
1520-5126
Publisher
American Chemical Society
Publication Date
Volume
132
Issue
35
Pages
12397–12403
Identifiers
DOI: 10.1021/ja103588w
PMID: 20718416
Source
Medline
License
Unknown

Abstract

Recent studies of organouranium chemistry have provided unusual pairs of similar polymetallic molecules containing (N)(3-) and (O)(2-) ligands, namely [(C(5)Me(5))U(mu-I)(2)](3)(mu(3)-N), 1, and [(C(5)Me(5))U(mu-I)(2)](3)(mu(3)-O), 2, and chair and boat conformations of [(C(5)Me(5))(2)U(mu-N)U(mu-N(3))(C(5)Me(5))(2)](4), 3. These compounds were analyzed by density functional theory and multiconfigurational quantum chemical studies to differentiate nitride versus oxide in molecules for which the crystallographic data were not definitive and to provide insight into the electronic structure and unique chemical bonding of these polymetallic compounds. Calculations were also performed on [(C(5)Me(5))(2)UN(3)(mu-N(3))](3), 4, and [(C(6)F(5))(3)BNU(N[Me]Ph)(3)], 5, for comparison with 1 and 3. On the basis of these results, the complex, [(C(5)Me(5))U(mu(3)-E)](8), 6, for which only low-quality X-ray crystallographic data are available, was analyzed to predict if E is nitride or oxide.

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