Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at UraniumCitation formats

  • External authors:
  • Benedict M Gardner
  • Christos E Kefalidis
  • Erli Lu
  • Dipti Patel
  • Ashley Wooles
  • Laurent Maron

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Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at Uranium. / Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; Mcinnes, Eric; Tuna, Floriana; Wooles, Ashley; Maron, Laurent; Liddle, Stephen.

In: Nature Communications, Vol. 8, 1898, 2017.

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Gardner, Benedict M ; Kefalidis, Christos E ; Lu, Erli ; Patel, Dipti ; Mcinnes, Eric ; Tuna, Floriana ; Wooles, Ashley ; Maron, Laurent ; Liddle, Stephen. / Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at Uranium. In: Nature Communications. 2017 ; Vol. 8.

Bibtex

@article{a30ed3f264304022b958773d02c9f2b2,
title = "Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at Uranium",
abstract = "Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here, we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction which satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests thatnitrenes are not generated and thus a reductive elimination has occurred. Though not optimallybalanced in this case, this work presents evidence that classical d-block redox chemistry can beperformed reversibly by f-block metals, and that uranium can thus mimic elementary transitionmetal reactivity, which may lead to the discovery of new f-block catalysis.",
author = "Gardner, {Benedict M} and Kefalidis, {Christos E} and Erli Lu and Dipti Patel and Eric Mcinnes and Floriana Tuna and Ashley Wooles and Laurent Maron and Stephen Liddle",
year = "2017",
doi = "10.1038/s41467-017-01363-0",
language = "English",
volume = "8",
journal = "Nature Communications",
issn = "2041-1723",
publisher = "Springer Nature",

}

RIS

TY - JOUR

T1 - Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at Uranium

AU - Gardner, Benedict M

AU - Kefalidis, Christos E

AU - Lu, Erli

AU - Patel, Dipti

AU - Mcinnes, Eric

AU - Tuna, Floriana

AU - Wooles, Ashley

AU - Maron, Laurent

AU - Liddle, Stephen

PY - 2017

Y1 - 2017

N2 - Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here, we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction which satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests thatnitrenes are not generated and thus a reductive elimination has occurred. Though not optimallybalanced in this case, this work presents evidence that classical d-block redox chemistry can beperformed reversibly by f-block metals, and that uranium can thus mimic elementary transitionmetal reactivity, which may lead to the discovery of new f-block catalysis.

AB - Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here, we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction which satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests thatnitrenes are not generated and thus a reductive elimination has occurred. Though not optimallybalanced in this case, this work presents evidence that classical d-block redox chemistry can beperformed reversibly by f-block metals, and that uranium can thus mimic elementary transitionmetal reactivity, which may lead to the discovery of new f-block catalysis.

U2 - 10.1038/s41467-017-01363-0

DO - 10.1038/s41467-017-01363-0

M3 - Article

VL - 8

JO - Nature Communications

JF - Nature Communications

SN - 2041-1723

M1 - 1898

ER -