Nickel Complexes of Carboxylate-Containing Polydentate Ligands as Models for the Active Site of Urease
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/141548
- author
- Carlsson, Håkan LU ; Haukka, Matti ; Bousseksou, Azzedine ; Latour, Jean-Marc and Nordlander, Ebbe LU
- organization
- publishing date
- 2004
- 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}}, }