TY - JOUR
T1 - DFT and CASPT2 analysis of polymetallic uranium nitride and oxide complexes
T2 - How theory can help when X-ray analysis is inadequate
AU - Todorova, Tanya K.
AU - Gagliardi, Laura
AU - Walensky, Justin R.
AU - Miller, Kevin A.
AU - Evans, William J.
PY - 2010/9/8
Y1 - 2010/9/8
N2 - Recent studies of organouranium chemistry have provided unusual pairs of similar polymetallic molecules containing (N)3- and (O)2- ligands, namely [(C5Me5)U(μ-I)2] 3(μ3-N), 1, and [(C5Me5)U(μ-I) 2]3(μ3-O), 2, and chair and boat conformations of [(C5Me5)2U(μ-N)U(μ- N3)(C5Me5)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 [(C5Me 5)2UN3(μ-N3)]3, 4, and [(C6F5)3BNU(N[Me]Ph)3], 5, for comparison with 1 and 3. On the basis of these results, the complex, [(C 5Me5)U(μ3-E)]8, 6, for which only low-quality X-ray crystallographic data are available, was analyzed to predict if E is nitride or oxide.
AB - Recent studies of organouranium chemistry have provided unusual pairs of similar polymetallic molecules containing (N)3- and (O)2- ligands, namely [(C5Me5)U(μ-I)2] 3(μ3-N), 1, and [(C5Me5)U(μ-I) 2]3(μ3-O), 2, and chair and boat conformations of [(C5Me5)2U(μ-N)U(μ- N3)(C5Me5)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 [(C5Me 5)2UN3(μ-N3)]3, 4, and [(C6F5)3BNU(N[Me]Ph)3], 5, for comparison with 1 and 3. On the basis of these results, the complex, [(C 5Me5)U(μ3-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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U2 - 10.1021/ja103588w
DO - 10.1021/ja103588w
M3 - Article
C2 - 20718416
AN - SCOPUS:77956241314
SN - 0002-7863
VL - 132
SP - 12397
EP - 12403
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 35
ER -