Oxo Group Protonation and Silylation of Pentavalent Uranyl Pacman Complexes

Arnold, Polly L.; Pécharman, Anne‐Frédérique; Love, Jason B.

doi:10.1002/ange.201104359

Cited by 10 publications

(8 citation statements)

References 38 publications

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“…Furthermore, we demonstrated that potassium or lithium base activation of the uranyl oxo groups promoted unprecedented UO-Si and UO-H bond forming reactions [14][15][16] . Outside of these examples, the formation of covalent oxygen-element bonds in uranyl chemistry remains restricted to a few discrete silyl complexes 17,18 .…”

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confidence: 97%

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Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation

et al. 2012

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The most common motif in uranium chemistry is the d(0)f(0) uranyl ion [UO(2)](2+) in which the oxo groups are rigorously linear and inert. Alternative geometries, such as the cis-uranyl, have been identified theoretically and implicated in oxo-atom transfer reactions that are relevant to environmental speciation and nuclear waste remediation. Single electron reduction is now known to impart greater oxo-group reactivity, but with retention of the linear OUO motif, and reactions of the oxo groups to form new covalent bonds remain rare. Here, we describe the synthesis, structure, reactivity and magnetic properties of a binuclear uranium-oxo complex. Formed through a combination of reduction and oxo-silylation and migration from a trans to a cis position, the new butterfly-shaped Si-OUO(2)UO-Si molecule shows remarkably strong U(V)-U(V) coupling and chemical inertness, suggesting that this rearranged uranium oxo motif might exist for other actinide species in the environment, and have relevance to the aggregation of actinide oxide clusters.

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Section: Main Textmentioning

confidence: 97%

“…although the presence of OH groups is implicit to this mechanism and would facilitate aggregation 16 .…”

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confidence: 99%

Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation

et al. 2012

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“…The ability of bare and ligated actinide cations to activate simple molecules has illuminated actinide-oxo ligand bonding and reactivity in both condensed and gas phases. [10][11][12][13][14][15][16][17][18][19] Among species of particular interest are the so-called actinyl ions, An V O2 + and An VI O2 2+ , which have distinctive linear OYL=An=OYL structures. [20][21][22] The general phenomenon of exchange of the oxygen atom in a water molecule with an oxygen atom in a metal complex, so-called oxo-exchange, provides evidence for activation of the metal oxide bond via water deprotonation and metal hydroxlation.…”

Section: Introductionmentioning

confidence: 99%

Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium

et al. 2019

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Swapping of an oxygen atom of water with that of a pentavalent actinide dioxide cation, AnO2 + also called an "actinyl", requires activation of an An-O bond. It was previously found that such oxo-exchange in gas phase occurs for the first two actinyls, PaO2 + and UO2 + , but not the next two, NpO2 + and PuO2 +. The An-O bond dissociation energies (BDEs) decrease from PaO2 + to PuO2 + , such that the observation of a parallel decrease in An-O bond reactivity is intriguing. To elucidate oxo-exchange, we here extend experimental studies to AmO2 + , americyl(V), and CmO2 + , curyl(V), which were produced in remarkable abundance by electrospray ionization of Am 3+ and Cm 3+ solutions. Like other AnO2 + , americyl(V) and curyl(V) adsorb up to four waters to form tetrahydrates AnO2(H2O)4 + with the actinide hexacoordinated by oxygens. It was found that AmO2 + does not oxo-exchange whereas CmO2 + does, establishing a "turn" to increasing reactivity from americyl to curyl, which validates computational predictions. Because oxo-exchange occurs via conversion of an actinyl(V) hydrate, AnO2(H2O) + , to an actinide(V) hydroxide, AnO(OH)2 + , it reflects the propensity for actinyl(V) hydrolysis: PaO2 + hydrolyzes and oxo-exchanges most easily, despite that it has the highest BDE of all AnO2 +. A reexamination of computational results for actinyl(V) oxo-exchange reveals distinctive properties and chemistry of Cm(V) species, particularly CmO(OH)2 + .

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“…Since this discovery, the reductive silylation of uranyl β‐ketoiminate complexes12 and their perfluoroborane adducts has been reported, but overall oxo functionalization reactions remain rare 8. 13 These oxo‐silylated complexes are stable indefinitely under anaerobic conditions, although little is known of their stability in air.…”

Section: Methodsmentioning

confidence: 99%

Controlled Deprotection and Reorganization of Uranyl Oxo Groups in a Binuclear Macrocyclic Environment

Jones¹,

Arnold²,

Love³

2012

Angewandte Chemie

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Anschalten der UV‐Reaktivität: Der silylierte Dioxouran(V)‐Komplex [(Me3SiOUO)2(L)2] (A) ist inert gegen Oxidation, kann aber nach Zweielektronenreduktion zu [(Me3SiOUO)2(L)]2− (1) zu [OU(μ‐O)2UO(L)2]2− (2) mit wiederhergestelltem Uranylcharakter desilyliert werden. Beim Entfernen der Silylgruppe zeigt sich eine neue Redox‐ und Oxoumlagerungschemie des Urans unter Rückbildung des Uranylmotivs sowie der Beteiligung des UVI/V‐Paars an einer Disauerstoffreduktion.

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Oxo Group Protonation and Silylation of Pentavalent Uranyl Pacman Complexes

Cited by 10 publications

References 38 publications

Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation

Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation

Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium

Controlled Deprotection and Reorganization of Uranyl Oxo Groups in a Binuclear Macrocyclic Environment

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