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Thermal and photochemical reduction and functionalization chemistry of the uranyl dication, [UVIO2]2+

Thermal and photochemical reduction and functionalization chemistry of the uranyl dication, [UVIO2]2+
Thermal and photochemical reduction and functionalization chemistry of the uranyl dication, [UVIO2]2+
The uranyl ion, [UVIO2]2+, possesses rigorously trans, strongly covalent, and chemically robust U-oxo groups. However, through the use of anaerobic reaction techniques, both one- and two-electron reductive functionalization of the uranyl oxo groups has been discovered and developed. Prior to 2010, this unusual reactivity centered around the reductive silylation of the uranyl ion which entailed conversion of the oxo ligands into siloxy ligands and reductive metalation of the uranyl oxo with Group 1 and f-block metals. This review surveys the large number of new examples of reductive functionalization of the uranyl ion that have been reported since 2010, including reductive borylation and alumination, metalation with d- or f-block metals, and new examples of reductive silylation. Other examples of oxo-group functionalization of [UVIO2]2+ that do not involve reduction, mainly with Group 1 cations, are also covered, along with new advances in the photochemistry of the uranyl(VI) ion that involve the transient formation of formally uranyl(V) [UVO2]+ ion.
0009-2665
10595-10637
Cowie, Bradley E.
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Purkis, Jamie M.
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Austin, Jonathan
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Love, Jason B.
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Arnold, Polly L.
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Cowie, Bradley E.
7f4df7e1-a008-4a6b-ab29-e8e9f95d78b7
Purkis, Jamie M.
17c76efb-2aa2-429e-92b3-5a21de7b02a5
Austin, Jonathan
9b92c945-1162-4785-ad11-c77f270cbf1d
Love, Jason B.
86349ecb-c5c7-4151-bd43-d79ddd214b27
Arnold, Polly L.
431d494e-712d-4677-9ee2-0bcefe8a5ca0

Cowie, Bradley E., Purkis, Jamie M., Austin, Jonathan, Love, Jason B. and Arnold, Polly L. (2019) Thermal and photochemical reduction and functionalization chemistry of the uranyl dication, [UVIO2]2+. Chemical Reviews, 119 (18), 10595-10637. (doi:10.1021/acs.chemrev.9b00048).

Record type: Article

Abstract

The uranyl ion, [UVIO2]2+, possesses rigorously trans, strongly covalent, and chemically robust U-oxo groups. However, through the use of anaerobic reaction techniques, both one- and two-electron reductive functionalization of the uranyl oxo groups has been discovered and developed. Prior to 2010, this unusual reactivity centered around the reductive silylation of the uranyl ion which entailed conversion of the oxo ligands into siloxy ligands and reductive metalation of the uranyl oxo with Group 1 and f-block metals. This review surveys the large number of new examples of reductive functionalization of the uranyl ion that have been reported since 2010, including reductive borylation and alumination, metalation with d- or f-block metals, and new examples of reductive silylation. Other examples of oxo-group functionalization of [UVIO2]2+ that do not involve reduction, mainly with Group 1 cations, are also covered, along with new advances in the photochemistry of the uranyl(VI) ion that involve the transient formation of formally uranyl(V) [UVO2]+ ion.

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acs.chemrev.9b00048 - Version of Record
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Published date: 12 August 2019

Identifiers

Local EPrints ID: 435930
URI: http://eprints.soton.ac.uk/id/eprint/435930
ISSN: 0009-2665
PURE UUID: f7394181-8cd5-495a-8545-fe8c8b2c042d
ORCID for Jamie M. Purkis: ORCID iD orcid.org/0000-0002-6387-1220

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Date deposited: 25 Nov 2019 17:30
Last modified: 26 Nov 2021 03:20

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Contributors

Author: Bradley E. Cowie
Author: Jamie M. Purkis ORCID iD
Author: Jonathan Austin
Author: Jason B. Love
Author: Polly L. Arnold

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