Dinuclear zinc(II) complexes with hydrogen bond donors as structural and functional phosphatase models

Bosch, Simone, Comba, Peter, Gahan, Lawrence R. and Schenk, Gerhard (2014) Dinuclear zinc(II) complexes with hydrogen bond donors as structural and functional phosphatase models. Inorganic Chemistry, 53 17: 9036-9051. doi:10.1021/ic5009945

Author Bosch, Simone
Comba, Peter
Gahan, Lawrence R.
Schenk, Gerhard
Title Dinuclear zinc(II) complexes with hydrogen bond donors as structural and functional phosphatase models
Journal name Inorganic Chemistry   Check publisher's open access policy
ISSN 1520-510X
Publication date 2014-09-02
Year available 2014
Sub-type Article (original research)
DOI 10.1021/ic5009945
Volume 53
Issue 17
Start page 9036
End page 9051
Total pages 16
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Formatted abstract
It is becoming increasingly apparent that the secondary coordination sphere can have a crucial role in determining the functional properties of biomimetic metal complexes. We have therefore designed and prepared a variety of ligands as metallo-hydrolase mimics, where hydrogen bonding in the second coordination sphere is able to influence the structure of the primary coordination sphere and the substrate binding. The assessment of a structure-function relationship is based on derivates of 2,6-bis{[bis(pyridin-2-ylmethyl)amino]methyl}-4- methylphenol (HBPMP = HL1) and 2-{[bis(pyridin-2-ylmethyl)amino] methyl}-6-{[(2-hydroxybenzyl)(pyridin-2-ylmethyl)amino]methyl}-4-methylphenol (H2BPBPMP = H2L5), well-known phenolate-based ligands for metallo-hydrolase mimics. The model systems provide similar primary coordination spheres but site-specific modifications in the secondary coordination sphere. Pivaloylamide and amine moieties were chosen to mimic the secondary coordination sphere of the phosphatase models, and the four new ligands H3L2, H3L3, HL4, and H4L6 vary in the type and geometric position of the H-bond donors and acceptors, responsible for the positioning of the substrate and release of the product molecules. Five dinuclear ZnII complexes were prepared and structurally characterized in the solid, and four also in solution. The investigation of the phosphatase activity of four model complexes illustrates the impact of the H-bonding network: the Michaelis-Menten constants (catalyst-substrate binding) for all complexes that support hydrogen bonding are smaller than for the reference complex, and this generally leads to higher catalytic efficiency and higher turnover numbers.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2015 Collection
School of Chemistry and Molecular Biosciences
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