Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319, USA.
Inorg Chem. 2009 Jul 20;48(14):6594-8. doi: 10.1021/ic9005696.
After reactions of uranium atoms with NF(3) and PF(3) to form the N[triple bond]UF(3) and P[triple bond]UF(3) molecules, the analogous reaction with AsF(3) produced the novel terminal arsenide As[triple bond]UF(3). This first molecule with a uranium-arsenic bond was identified from matrix infrared spectra through comparison with spectra of the uranium nitride and phosphide species, with spectra using other metals, and with frequencies computed by density functional and multiconfigurational wave function methods. The latter calculation describes a weak triple bond to uranium in the As[triple bond]UF(3) molecule, which has slightly less bonding and more antibonding character than the weak triple bond in P[triple bond]UF(3).
在铀原子与 NF(3) 和 PF(3) 反应形成 N[三键]UF(3) 和 P[三键]UF(3) 分子后，与 AsF(3) 的类似反应生成了新型末端砷化物 As[三键]UF(3)。通过与氮化物和磷化物物种的光谱、使用其他金属的光谱以及通过密度泛函和多组态波函数方法计算的频率进行比较，从基质红外光谱中鉴定出具有铀-砷键的第一个分子。后一种计算方法描述了 As[三键]UF(3) 分子中与铀的弱三键，该键的成键性略低于 P[三键]UF(3)中的弱三键，反键性则稍强。
