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Bioinorganic Chemistry of Group 12 Complexes Supported by Tetradentate Tripodal Ligands Having Internal Hydrogen‐Bond Donors
Author(s) -
Berreau Lisa M.
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500886
Subject(s) - chemistry , alkoxide , reactivity (psychology) , amide , hydrogen bond , deprotonation , zinc , bond cleavage , medicinal chemistry , bioinorganic chemistry , hydrolysis , polymer chemistry , stereochemistry , molecule , organic chemistry , catalysis , medicine , ion , alternative medicine , pathology
Inspired 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 CO 2 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 p K a 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 CO 2 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)