Issue 14, 2010

Equatorial ligand substitution by hydroxide in uranyl Pacman complexes of a Schiff-base pyrrolemacrocycle

Abstract

The synthesis of the mono-uranyl complex [UO2(THF)(H2LMe)] of a ditopic Schiff-base pyrrole macrocycle is described and is shown to adopt a Pacman wedge-shaped structure in which the uranyl dication is desymmetrised and sits solely in one N4-donor compartment to leave the other vacant. While investigating the mechanism of the previously reported, base-initiated, reductive silylation chemistry of [UO2(THF)(H2LMe)], we found that uranyl hydroxide complexes could be isolated. As such, the reaction between [UO2(THF)(H2LMe)] and KH in THF generated the dimeric cation-cation hydroxide [{UO2(OH)K(C6H6)(H2LMe)}2] when crystallised from C6H6, or alternatively, when crystallised from THF, the monomeric THF-adducted cation-cation complex [UO2(OH)K(THF)2(H2LMe)] was isolated. These compounds result formally from the substitution of the equatorial THF molecule by hydroxide, and it was also shown that the reaction between dry KOH and [UO2(THF)(H2LMe)] generated [{UO2(OH)K(C6H6)(H2LMe)}2].

Graphical abstract: Equatorial ligand substitution by hydroxide in uranyl Pacman complexes of a Schiff-base pyrrole macrocycle

Supplementary files

Article information

Article type
Paper
Submitted
22 Oct 2009
Accepted
12 Feb 2010
First published
02 Mar 2010

Dalton Trans., 2010,39, 3501-3508

Equatorial ligand substitution by hydroxide in uranyl Pacman complexes of a Schiff-base pyrrole macrocycle

P. L. Arnold, D. Patel, A. Pécharman, C. Wilson and J. B. Love, Dalton Trans., 2010, 39, 3501 DOI: 10.1039/B922115H

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