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

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

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, tetrava...

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Veröffentlicht in:Journal of the American Chemical Society 2020-04, Vol.142 (16), p.7368-7373
Hauptverfasser: Rice, Natalie T, McCabe, Karl, Bacsa, John, Maron, Laurent, La Pierre, Henry S
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container_issue 16
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container_title Journal of the American Chemical Society
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creator Rice, Natalie T
McCabe, Karl
Bacsa, John
Maron, Laurent
La Pierre, Henry S
description 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.
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title Two-Electron Oxidative Atom Transfer at a Homoleptic, Tetravalent Uranium Complex
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