Rice Natalie T, McCabe Karl, Bacsa John, Maron Laurent, La Pierre Henry S
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, United States.
Laboratoire de Physique et Chimie des Nano-objets, Institut National des Sciences Appliquees, 31077 Toulouse, Cedex 4 France.
J Am Chem Soc. 2020 Apr 22;142(16):7368-7373. doi: 10.1021/jacs.0c02693. Epub 2020 Apr 9.
A tetrahomoleptic, pseudotetrahedral U imidophosphorane complex, [U(NP(pip))], , is reported. This complex can be oxidized by two electrons with either mesityl azide or nitrous oxide. This two-electron atom/group transfer oxidation is the first example observed at a homoleptic, tetravalent uranium complex. The mesityl imido compound [U(NMes)(NP(pip))], , exhibits a unique square pyramidal geometry in contrast to the expected trigonal bipyramidal geometry of the oxo complex [U(O)(NP(pip))], . The bonding driving the structural dichotomy of these structures and the absence of a structurally observable inverse -influence in were examined by DFT and natural bonding orbital analysis.
报道了一种四同配体的假四面体铀亚磷酰亚胺配合物[U(NP(pip))]。该配合物可被均三甲苯叠氮化物或一氧化二氮氧化两个电子。这种双电子原子/基团转移氧化是在同配体四价铀配合物中观察到的首例。与氧代配合物[U(O)(NP(pip))]预期的三角双锥几何构型不同，均三甲苯亚胺化合物[U(NMes)(NP(pip))]呈现出独特的四方锥几何构型。通过密度泛函理论（DFT）和自然键轨道分析研究了驱动这些结构结构二分法的键合以及[U(NMes)(NP(pip))]中结构上不可观察到的反位影响的缺失。
