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Nickel Complexes of Carboxylate-Containing Polydentate Ligands as Models for the Active Site of Urease

Carlsson, Håkan LU orcid ; Haukka, Matti ; Bousseksou, Azzedine ; Latour, Jean-Marc and Nordlander, Ebbe LU (2004) In Inorganic Chemistry 43(26). p.8252-8262
Abstract
Two new carboxylate-containing polydentate ligands have been synthesized, the symmetric ligand 2,6-bis[N-(N-(carboxylmethyl)-N-((1-methylimidazol)methyl)amine)methyl]-4-methylphenolate (BCIMP) and the corresponding asymmetric ligand 2-(N-isopropyl-N-((1-aminomethyl)-4-methylphenol (ICIMP). The ligands have been used to prepare model complexes for the active site of the dinuclear nickel enzyme urease, viz. [Ni2(BCIMP)Ac2]- (6), [Ni2(BCIMP)(Ph2Ac)2]- (7), [Ni2(ICIMP)(Ph2Ac)2] (14), [Ni4(ICIMP)2(Ph2Ac)2][ClO4]2 (15), [Ni4(ICIMP)2(Ph2Ac)2(DMF)2][ClO4]2 (16), and [Ni4(ICIMP)2(Ph2Ac)2(urea)(H2O)][ClO4]2 (17), where the latter complex contains urea coordinated in a unidentate fashion through the carbonyl oxygen. The N2O-N2O2 donor set of ICIMP... (More)
Two new carboxylate-containing polydentate ligands have been synthesized, the symmetric ligand 2,6-bis[N-(N-(carboxylmethyl)-N-((1-methylimidazol)methyl)amine)methyl]-4-methylphenolate (BCIMP) and the corresponding asymmetric ligand 2-(N-isopropyl-N-((1-aminomethyl)-4-methylphenol (ICIMP). The ligands have been used to prepare model complexes for the active site of the dinuclear nickel enzyme urease, viz. [Ni2(BCIMP)Ac2]- (6), [Ni2(BCIMP)(Ph2Ac)2]- (7), [Ni2(ICIMP)(Ph2Ac)2] (14), [Ni4(ICIMP)2(Ph2Ac)2][ClO4]2 (15), [Ni4(ICIMP)2(Ph2Ac)2(DMF)2][ClO4]2 (16), and [Ni4(ICIMP)2(Ph2Ac)2(urea)(H2O)][ClO4]2 (17), where the latter complex contains urea coordinated in a unidentate fashion through the carbonyl oxygen. The N2O-N2O2 donor set of ICIMP provides a good framework for the preparation of urease models, but in some cases tetranuclear nickel complexes are formed due to coordination of the carboxylate moiety of one dinickel-ICIMP unit to one or both of the nickels of a second Ni2 unit. Reactivity and kinetics studies of 7 and 15 show that these model complexes catalyze hydrolysis of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) at basic pH. In this assay, complexes based on the asymmetric ligand ICIMP exhibit a significantly faster rate of hydrolysis than the corresponding BCIMP complexes. Magnetic measurements indicate that there are weak antiferromagnetic interactions between the nickel ions in complex 16. (Less)
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author
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Inorganic Chemistry
volume
43
issue
26
pages
8252 - 8262
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:15606171
  • wos:000225906700017
  • scopus:11144277364
ISSN
1520-510X
DOI
10.1021/ic049048u
language
English
LU publication?
yes
id
b550d03a-b992-4d78-bd50-5e3cc58cac78 (old id 141548)
date added to LUP
2016-04-01 12:20:42
date last changed
2022-04-13 17:44:29
@article{b550d03a-b992-4d78-bd50-5e3cc58cac78,
  abstract     = {{Two new carboxylate-containing polydentate ligands have been synthesized, the symmetric ligand 2,6-bis[N-(N-(carboxylmethyl)-N-((1-methylimidazol)methyl)amine)methyl]-4-methylphenolate (BCIMP) and the corresponding asymmetric ligand 2-(N-isopropyl-N-((1-aminomethyl)-4-methylphenol (ICIMP). The ligands have been used to prepare model complexes for the active site of the dinuclear nickel enzyme urease, viz. [Ni2(BCIMP)Ac2]- (6), [Ni2(BCIMP)(Ph2Ac)2]- (7), [Ni2(ICIMP)(Ph2Ac)2] (14), [Ni4(ICIMP)2(Ph2Ac)2][ClO4]2 (15), [Ni4(ICIMP)2(Ph2Ac)2(DMF)2][ClO4]2 (16), and [Ni4(ICIMP)2(Ph2Ac)2(urea)(H2O)][ClO4]2 (17), where the latter complex contains urea coordinated in a unidentate fashion through the carbonyl oxygen. The N2O-N2O2 donor set of ICIMP provides a good framework for the preparation of urease models, but in some cases tetranuclear nickel complexes are formed due to coordination of the carboxylate moiety of one dinickel-ICIMP unit to one or both of the nickels of a second Ni2 unit. Reactivity and kinetics studies of 7 and 15 show that these model complexes catalyze hydrolysis of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) at basic pH. In this assay, complexes based on the asymmetric ligand ICIMP exhibit a significantly faster rate of hydrolysis than the corresponding BCIMP complexes. Magnetic measurements indicate that there are weak antiferromagnetic interactions between the nickel ions in complex 16.}},
  author       = {{Carlsson, Håkan and Haukka, Matti and Bousseksou, Azzedine and Latour, Jean-Marc and Nordlander, Ebbe}},
  issn         = {{1520-510X}},
  language     = {{eng}},
  number       = {{26}},
  pages        = {{8252--8262}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Inorganic Chemistry}},
  title        = {{Nickel Complexes of Carboxylate-Containing Polydentate Ligands as Models for the Active Site of Urease}},
  url          = {{http://dx.doi.org/10.1021/ic049048u}},
  doi          = {{10.1021/ic049048u}},
  volume       = {{43}},
  year         = {{2004}},
}