Issue 8, 2013

Ligand displacement for fixing manganese: relevance to cellular metal ion transport and synthesis of polymeric coordination complexes

Abstract

A dinuclear manganese(III) complex (1) of an N-(carboxymethyl)-N-[3,5-bis(α,α-dimethylbenzyl-2-hydroxybenzyl)]glycine (HDA) ligand (L) binds a manganese(II) species through displacement of its solvating ligands by appropriately dispositioned carbonyl groups of a dinuclear complex {[Mn2(L)2(OH)(OCH3)][Mn(H2O)3(CH3OH)3], 2, triclinic P[1 with combining macron], a = 13.172(3) Å, b = 15.897(3) Å, c = 19.059(4) Å, V = 3461.9(13) Å3} leading to a trinuclear complex {3, monoclinic P21/n, a = 11.7606(8) Å, b = 21.3505(8) Å, c = 26.7827(17) Å, V = 6722.7(7) Å3} with cyclization of two of the carboxy groups through the doubly-carboxy group coordinated Mn2+ ion. The reaction is discussed in terms of its significance as an illustration of how Mn2+ ions might be sequestered in biological systems. A similar solvato-ligand displacement reaction was used to synthesise coordination polymers of an HDA iron(III) complex involving polymerization through a bridging carboxylato group. Several isostructural polymers (5–7; for 5: orthorhombic Pbca, a = 9.411(5) Å, b = 16.390(8) Å, c = 37.968(19) Å, V = 5856(5) Å3) with different coordinated alcohols could be prepared indicating the potential synthetic uses of this method.

Graphical abstract: Ligand displacement for fixing manganese: relevance to cellular metal ion transport and synthesis of polymeric coordination complexes

Supplementary files

Article information

Article type
Paper
Submitted
24 Oct 2012
Accepted
28 Nov 2012
First published
04 Dec 2012

Dalton Trans., 2013,42, 2779-2785

Ligand displacement for fixing manganese: relevance to cellular metal ion transport and synthesis of polymeric coordination complexes

N. M. Sanchez-Ballester, L. K. Shrestha, M. R. J. Elsegood, W. Schmitt, K. Ariga, C. E. Anson, J. P. Hill and A. K. Powell, Dalton Trans., 2013, 42, 2779 DOI: 10.1039/C2DT32547K

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