Department of Chemistry and Pharmacy, Inorganic Chemistry, University of Erlangen-Nuremberg, Egerlandstrasse 1, D-91058 Erlangen, Germany.
Inorg Chem. 2012 Jun 4;51(11):6190-9. doi: 10.1021/ic300273d. Epub 2012 May 16.
An inverse trans influence has been observed in a high-valent U(V) imide complex, [(((Ad)ArO)(3)N)U(NMes)]. A thorough theoretical evaluation has been employed in order to corroborate the ITI in this unusual complex. Computations on the target complex, [(((Ad)ArO)(3)N)U(NMes)], and the model complexes [(((Me)ArO)(3)N)U(NMes)] and [(NMe(3))(OMe(2))(OMe)(3)U(NPh)] are discussed along with synthetic details and supporting spectroscopic data. Additionally, the syntheses and full characterization data of the related U(V) trimethylsilylimide complex [(((Ad)ArO)(3)N)U(NTMS)] and U(IV) azide complex [(((Ad)ArO)(3)N)U(N(3))] are also presented for comparison.
在高价 U(V)亚胺配合物 [(((Ad)ArO)(3)N)U(NMes)]中观察到了逆瞬变影响。为了证实这种不寻常配合物中的 ITI，我们进行了彻底的理论评估。讨论了目标配合物 [(((Ad)ArO)(3)N)U(NMes)]以及模型配合物 [(((Me)ArO)(3)N)U(NMes)]和 [(NMe(3))(OMe(2))(OMe)(3)U(NPh)]的计算，并提供了合成细节和支持的光谱数据。此外，还介绍了相关的 U(V)三甲基硅亚胺配合物 [(((Ad)ArO)(3)N)U(NTMS)]和 U(IV)叠氮化物配合物 [(((Ad)ArO)(3)N)U(N(3))]的合成及全谱学数据，以便进行比较。
