Abstract
AbstractInspired by the proposed role of secondary hydrogen‐bonding interactions in modulating the chemistry of mononuclear zinc centers in metalloenzymes, zinc complexes supported by tetradentate tripodal ligands having one or more internal hydrogen‐bond donors have been prepared, characterized, and investigated for biologically relevant reactivity. Complexes of this class have been examined in terms of water activation and CO2 reactivity, alcohol/alkoxide coordination, and amide methanolysis and phosphate ester hydrolysis reactivity. The results of these studies indicate that the presence of internal hydrogen‐bond donors will lower the pKa of a zinc‐bound water molecule, stabilize zinc alkoxide species with respect to hydrolysis, and enhance the phosphate ester cleavage reactivity of mononuclear zinc complexes. In addition, use of tripodal ligands having a single internal hydrogen‐bond donor has enabled the isolation of a novel cadmium hydroxide complex and examination of its CO2 chemistry, as well as the identification of a novel amide cleavage reaction which proceeds by initial formation of a deprotonated amide intermediate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
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