Selective Coordination of Gallium(III), Zinc(II), and Copper(II) by an Asymmetric Dinucleating Ligand: A Model for Metallophosphatases.

Bosch, Simone, Comba, Peter, Gahan, Lawrence R., Hanson, Graeme R., Noble, Christopher, Schenk, Gerhard and Wadepohl, Hubert (2015) Selective Coordination of Gallium(III), Zinc(II), and Copper(II) by an Asymmetric Dinucleating Ligand: A Model for Metallophosphatases.. Chemistry - A European Journal, 21 50: 18269-18279. doi:10.1002/chem.201503348


Author Bosch, Simone
Comba, Peter
Gahan, Lawrence R.
Hanson, Graeme R.
Noble, Christopher
Schenk, Gerhard
Wadepohl, Hubert
Title Selective Coordination of Gallium(III), Zinc(II), and Copper(II) by an Asymmetric Dinucleating Ligand: A Model for Metallophosphatases.
Journal name Chemistry - A European Journal   Check publisher's open access policy
ISSN 0947-6539
1521-3765
Publication date 2015-11-18
Year available 2015
Sub-type Article (original research)
DOI 10.1002/chem.201503348
Open Access Status Not Open Access
Volume 21
Issue 50
Start page 18269
End page 18279
Total pages 12
Place of publication Weinheim, Germany
Publisher Wiley - V C H Verlag GmbH
Collection year 2016
Language eng
Formatted abstract
Complexation studies of the dinucleating ligand H3L (H3L=2-{[bis(pyridin-2-ylmethyl)amino]methyl}-6-{[bis(6-pivaloylamidopyridin-2-ylmethyl)amino]methyl}-4-methylphenol), with metal-binding sites A and B, which both provide four donors to a metal ion; a tertiary amine; two pyridines (substituted with amide hydrogen-bond donors in site B), and a bridging phenolate, with ZnII, CuII, and GaIII are reported. The titration of H3L with the three metal ions in solution was monitored by NMR spectroscopy or EPR and UV/Vis/near-IR spectroscopy, as well as by ESI-MS to analyze the selectivity of the two metal-ion sites A and B of this model ligand for metallophosphatases; the spectroscopic assignments are supported by X-ray crystallography results. The first ZnII ion coordinates to site A with unsubstituted pyridine donors and, upon addition of a second equivalent of ZnII, this coordinates to the sterically less accessible site B. From a similar titration with GaIII, it emerges that only a mononuclear complex is obtained, with the GaIII center coordinated to site A. When one equivalent of GaIII is reacted with the mononuclear ZnII complex, ZnII is forced by GaIII to exchange the site; this results in a dinuclear complex with GaIII in site A and ZnII in site B. With CuII, two isomers are observed: one with and the other without a bridging phenolate; these differ significantly in their spectroscopic and magnetic properties.
Keyword X ray diffraction
Ligands
Metalloenzymes
Structure Elucidation
Transition Metals
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2016 Collection
School of Chemistry and Molecular Biosciences
Centre for Advanced Imaging Publications
 
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Created: Fri, 20 Nov 2015, 13:40:35 EST by Mrs Louise Nimwegen on behalf of School of Chemistry & Molecular Biosciences