Bioinspired Hydrogen Bond Motifs in Ligand Design: The Role of Noncovalent Interactions in Metal Ion Mediated Activation of Dioxygen
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- 4 December 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 38 (1), 54-61
- https://doi.org/10.1021/ar030160q
Abstract
Hydrogen bonds influence secondary coordination spheres around metal ions in many proteins. To duplicate these features of molecular architecture in synthetic systems, urea-based ligands have have been developed that create rigid organic frameworks when bonded to metal ions. These frameworks position hydro-gen bond donors proximal to metal ion(s) to form specific chem-ical microenvironments. Iron(II) and manganese(II) complexes with constrained cavities activate O2, yielding MIII (MIII = Fe and Mn) complexes with terminal oxo ligands. Installation of anionic sites within the cavity assists the formation of complexes with MII/III−OH and MIII−O units derived directly from water. Opening the cavity promotes M(μ-O)2M rhombs, as illustrated by isolation of a cobalt(III) analogue, the stability of which is promoted by the hydrogen bonds surrounding the bridging oxo ligands.Keywords
This publication has 55 references indexed in Scilit:
- Monomeric MnIII/II and FeIII/II Complexes with Terminal Hydroxo and Oxo Ligands: Probing Reactivity via O−H Bond Dissociation EnergiesJournal of the American Chemical Society, 2003
- Hydrogen Bonds around M(μ‐O)2M Rhombs: Stabilizing a {CoIII(μ‐O)2CoIII} Complex at Room TemperatureAngewandte Chemie International Edition, 2003
- Novel Insights into the Basis for Escherichia coli Superoxide Dismutase's Metal Ion Specificity from Mn-Substituted FeSOD and Its Very High EmBiochemistry, 2001
- Investigations of the Roles of the Distal Heme Environment and the Proximal Heme Iron Ligand in Peroxide Activation by Heme Enzymes via Molecular Engineering of MyoglobinAccounts of Chemical Research, 2001
- Hydrogen Bonding in Metal Oxo Complexes: Synthesis and Structure of a Monomeric Manganese(III)−Oxo Complex and Its Hydroxo AnalogueJournal of the American Chemical Society, 2000
- Effects of Concerted Hydrogen Bonding of Distal Histidine on Active Site Structures of Horseradish Peroxidase. Resonance Raman Studies with Asn70 MutantsJournal of the American Chemical Society, 1997
- Heme-Containing OxygenasesChemical Reviews, 1996
- Designing Ligands for Oxidizing ComplexesAccounts of Chemical Research, 1994
- Dioxygen Binding in Iron and Cobalt Picnic Basket PorphyrinsJournal of the American Chemical Society, 1994
- Bond dissociation energies in DMSO related to the gas phase valuesJournal of the American Chemical Society, 1991