Uranium(III) coordination chemistry and oxidation in a flexible small-cavity macrocycle

Arnold, P. L., Farnaby, J. H. , Gardiner, M. G. and Love, J. B. (2015) Uranium(III) coordination chemistry and oxidation in a flexible small-cavity macrocycle. Organometallics, 34(11), pp. 2114-2117. (doi: 10.1021/om5012193)

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Abstract

U(III) complexes of the conformationally flexible, small-cavity macrocycle trans-calix[2]benzene[2]pyrrolide (L)2–, [U(L)X] (X = O-2,6-tBu2C6H3, N(SiMe3)2), have been synthesized from [U(L)BH4] and structurally characterized. These complexes show binding of the U(III) center in the bis(arene) pocket of the macrocycle, which flexes to accommodate the increase in the steric bulk of X, resulting in long U–X bonds to the ancillary ligands. Oxidation to the cationic U(IV) complex [U(L)X][B(C6F5)4] (X = BH4) results in ligand rearrangement to bind the smaller, harder cation in the bis(pyrrolide) pocket, in a conformation that has not been previously observed for (L)2–, with X located between the two ligand arene rings.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Farnaby, Dr Joy
Authors: Arnold, P. L., Farnaby, J. H., Gardiner, M. G., and Love, J. B.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Organometallics
Publisher:American Chemical Society
ISSN:0276-7333
ISSN (Online):1520-6041
Published Online:20 January 2015
Copyright Holders:Copyright © 2015 American Chemical Society
First Published:First published in Organometallics 34(11): 2114-2117
Publisher Policy:Reproduced in accordance with the publisher copyright policy

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