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Dimetal complexes of a bibrachial 2+2 thiolate-based macrocycle

Journal article
Authors Anders Lennartson
Vickie McKee
Jane Nelson
Michael Arthurs
Christine J. McKenzie
Published in Supramolecular Chemistry
Volume 24
Pages 604-617
ISSN 10610278
Publication year 2012
Published at
Pages 604-617
Language en
Keywords cryptand, dimetallic, macrocycle, thiophenol, tren
Subject categories Chemical Sciences

Abstract

Protocols for accessing the [2+3] and [2+2] tren + thiophenolate-based cryptands and macrocycles, respectively, have been devised; however, a propensity towards incomplete crypt formation is clear: Cd(II)2, Mn(II)2, Ni(II)2 and Pd(II)2 complexes of the [2+2] bibrachial systems in which one arm of each of the tren head groups is pendant were isolated in attempts to make the crypts. The Mn(II)2 complex can be used in transmetallation reactions and these probably occur in a stepwise fashion for the heavier, softer metal ions since the plausible intermediates Mn(II)M(II), M = Cd, Pd, were identified. There is evidence for the formation of [2+3] cryptand systems using templating Ag(I) and Cd(II); however, reaction conditions need to be strictly controlled to ensure isolation of either the [2+3] cryptand or the [2+2] macrocyclic complex since ensuing reactions leading to intractable oligomers are competing. The template and transmetallation experiments described here emphasise the relatively greater hydrolytic sensitivity of the thiophenol-derived imino macrocycles and crypts than their better-known phenol-based counterparts. © 2012 Copyright Taylor and Francis Group, LLC.

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