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Issue 15, 2019
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Applications of boroxide ligands in supporting small molecule activation by U(iii) and U(iv) complexes

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Abstract

The boroxide ligand [OBAr2] (Ar = Mes, Trip) is shown to be able to support both UIII and UIV centres for the first time. The synthesis and structures of homoleptic and heteroleptic UIII and UIV complexes are reported. The UX3 complex with larger substituents, [U(OBTrip2)3]2, exhibits greater thermal stability compared to less encumbered [U(OBMes2)3]2 but reacts with a smaller range of the small molecules tested to date. Initial studies on their capacity to participate in small molecule chemistry show that dark purple [U(OBMes2)3]2 binds and/or reductively activates a variety of small molecules such as pyridine-oxide, triphenylphosphineoxide, sulfur, and dicyclohexylcarbodiimide. While [U(OBMes2)3]2 shows no reaction with CO or CO2, [U(OBTrip2)3]2 is oxidised by both, in the former case forming [U(OBTrip2)4], and in the latter case forming a small quantity of the structurally characterised μ-carbonate product [(μ-CO3){U(OBTrip2)3}2].

Graphical abstract: Applications of boroxide ligands in supporting small molecule activation by U(iii) and U(iv) complexes

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Supplementary files

Article information


Submitted
21 Dec 2018
Accepted
28 Feb 2019
First published
29 Mar 2019

This article is Open Access

Dalton Trans., 2019,48, 4894-4905
Article type
Paper

Applications of boroxide ligands in supporting small molecule activation by U(III) and U(IV) complexes

P. L. Arnold, L. Puig-Urrea, J. A. L. Wells, D. Yuan, F. L. Cruickshank and R. D. Young, Dalton Trans., 2019, 48, 4894
DOI: 10.1039/C8DT05051A

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