Ligand displacement for fixing manganese: relevance to cellular metal ion transport and synthesis of polymeric coordination complexesElectronic supplementary information (ESI) available: CIFs for compounds 2, 3, 5-7; additional figures of compounds 6 and 7. CCDC 893592, 893593, 893594, 893595, 906345. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt32547k

• Main Authors: Sanchez-Ballester, Noelia M, Shrestha, Lok Kumar, Elsegood, Mark R. J, Schmitt, Wolfgang, Ariga, Katsuhiko, Anson, Christopher E, Hill, Jonathan P, Powell, Annie K
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c2dt32547k

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 {[Mn 2 (L) 2 (OH)(OCH 3 )][Mn(H 2 O) 3 (CH 3 OH) 3 ], 2 , triclinic P 1&cmb.macr;, a = 13.172(3) Å, b = 15.897(3) Å, c = 19.059(4) Å, V = 3461.9(13) Å 3 } leading to a trinuclear complex { 3 , monoclinic P 21/ n , a = 11.7606(8) Å, b = 21.3505(8) Å, c = 26.7827(17) Å, V = 6722.7(7) Å 3 } with cyclization of two of the carboxy groups through the doubly-carboxy group coordinated Mn 2+ ion. The reaction is discussed in terms of its significance as an illustration of how Mn 2+ 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) Å 3 ) with different coordinated alcohols could be prepared indicating the potential synthetic uses of this method. A dinuclear manganese ( iii ) complex binds a third manganese through peripheral carbonyl groups.