Two-Electron Oxidative Atom Transfer at a Homoleptic, Tetravalent Uranium Complex

Natalie T Rice; Karl McCabe; John Bacsa; Laurent Maron; Henry S La Pierre

doi:10.1021/jacs.0c02693

Two-Electron Oxidative Atom Transfer at a Homoleptic, Tetravalent Uranium Complex

J Am Chem Soc. 2020 Apr 22;142(16):7368-7373. doi: 10.1021/jacs.0c02693. Epub 2020 Apr 9.

Authors

Natalie T Rice¹, Karl McCabe², John Bacsa¹, Laurent Maron², Henry S La Pierre^{1

3}

Affiliations

¹ School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, United States.
² Laboratoire de Physique et Chimie des Nano-objets, Institut National des Sciences Appliquees, 31077 Toulouse, Cedex 4 France.
³ Nuclear and Radiological Engineering and Medical Physics Program, School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, United States.

PMID: 32248676
DOI: 10.1021/jacs.0c02693

Abstract

A tetrahomoleptic, pseudotetrahedral U⁴⁺ imidophosphorane complex, [U(NP(pip)₃)₄], 1-U(PN), 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)₃)₄], 2-U(PN)NMes, exhibits a unique square pyramidal geometry in contrast to the expected trigonal bipyramidal geometry of the oxo complex [U(O)(NP(pip)₃)₄], 2-U(PN)O. The bonding driving the structural dichotomy of these structures and the absence of a structurally observable inverse trans-influence in 2-U(PN)NMes were examined by DFT and natural bonding orbital analysis.