Unsymmetrical dizinc complexes as models for the active sites of phosphohydrolases.
(2010) In Dalton Transactions 39(35). p.8183-8194- Abstract
- The unsymmetrical dinucleating ligand 2-(N-isopropyl-N-((2-pyridyl)methyl)aminomethyl)-6-(N-(carboxylmethyl)-N-((2-pyridyl)methyl)aminomethyl)-4-methylphenol (IPCPMP or L) has been synthesized to model the active site environment of dinuclear metallohydrolases. It has been isolated as the hexafluorophosphate salt H(4)IPCPMP(PF(6))(2).2H(2)O (H(4)L), which has been structurally characterized, and has been used to form two different Zn(ii) complexes, [{Zn(2)(IPCPMP)(OAc)}(2)][PF(6)](2) () and [{Zn(2)(IPCPMP)(Piv)}(2)][PF(6)](2) () (OAc = acetate; Piv = pivalate). The crystal structures of and show that they consist of tetranuclear complexes with very similar structures. Infrared spectroscopy and mass spectrometry indicate that the... (More)
- The unsymmetrical dinucleating ligand 2-(N-isopropyl-N-((2-pyridyl)methyl)aminomethyl)-6-(N-(carboxylmethyl)-N-((2-pyridyl)methyl)aminomethyl)-4-methylphenol (IPCPMP or L) has been synthesized to model the active site environment of dinuclear metallohydrolases. It has been isolated as the hexafluorophosphate salt H(4)IPCPMP(PF(6))(2).2H(2)O (H(4)L), which has been structurally characterized, and has been used to form two different Zn(ii) complexes, [{Zn(2)(IPCPMP)(OAc)}(2)][PF(6)](2) () and [{Zn(2)(IPCPMP)(Piv)}(2)][PF(6)](2) () (OAc = acetate; Piv = pivalate). The crystal structures of and show that they consist of tetranuclear complexes with very similar structures. Infrared spectroscopy and mass spectrometry indicate that the tetranuclear complexes dissociate into dinuclear complexes in solution. Potentiometric studies of the Zn(ii) : IPCPMP system in aqueous solution reveal that a mononuclear complex is surprisingly stable at low pH, even at a 2 : 1 Zn(ii) : L ratio, but a dinuclear complex dominates at high pH and transforms into a dihydroxido complex by a cooperative deprotonation of two, probably terminally coordinated, water molecules. A kinetic investigation indicates that one of these hydroxides is the active nucleophile in the hydrolysis of bis(2,4-dinitrophenyl)phosphate (BDNPP) enhanced by complex , and mechanistic proposals are presented for this reaction as well as the previously reported transesterification of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) promoted by Zn(ii) complexes of IPCPMP. (Less)
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https://lup.lub.lu.se/record/1665608
- author
- Jarenmark, Martin LU ; Csapó, Edit ; Singh, Jyoti LU ; Wöckel, Simone ; Farkas, Etelka ; Meyer, Franc ; Haukka, Matti and Nordlander, Ebbe LU
- organization
- publishing date
- 2010
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Dalton Transactions
- volume
- 39
- issue
- 35
- pages
- 8183 - 8194
- publisher
- Royal Society of Chemistry
- external identifiers
-
- wos:000281230700011
- pmid:20683537
- scopus:77955930231
- pmid:20683537
- ISSN
- 1477-9234
- DOI
- 10.1039/b925563j
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
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- 7c60f491-c019-4524-8af3-948884fab281 (old id 1665608)
- date added to LUP
- 2016-04-01 10:30:36
- date last changed
- 2022-04-12 06:56:06
@article{7c60f491-c019-4524-8af3-948884fab281,
abstract = {{The unsymmetrical dinucleating ligand 2-(N-isopropyl-N-((2-pyridyl)methyl)aminomethyl)-6-(N-(carboxylmethyl)-N-((2-pyridyl)methyl)aminomethyl)-4-methylphenol (IPCPMP or L) has been synthesized to model the active site environment of dinuclear metallohydrolases. It has been isolated as the hexafluorophosphate salt H(4)IPCPMP(PF(6))(2).2H(2)O (H(4)L), which has been structurally characterized, and has been used to form two different Zn(ii) complexes, [{Zn(2)(IPCPMP)(OAc)}(2)][PF(6)](2) () and [{Zn(2)(IPCPMP)(Piv)}(2)][PF(6)](2) () (OAc = acetate; Piv = pivalate). The crystal structures of and show that they consist of tetranuclear complexes with very similar structures. Infrared spectroscopy and mass spectrometry indicate that the tetranuclear complexes dissociate into dinuclear complexes in solution. Potentiometric studies of the Zn(ii) : IPCPMP system in aqueous solution reveal that a mononuclear complex is surprisingly stable at low pH, even at a 2 : 1 Zn(ii) : L ratio, but a dinuclear complex dominates at high pH and transforms into a dihydroxido complex by a cooperative deprotonation of two, probably terminally coordinated, water molecules. A kinetic investigation indicates that one of these hydroxides is the active nucleophile in the hydrolysis of bis(2,4-dinitrophenyl)phosphate (BDNPP) enhanced by complex , and mechanistic proposals are presented for this reaction as well as the previously reported transesterification of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) promoted by Zn(ii) complexes of IPCPMP.}},
author = {{Jarenmark, Martin and Csapó, Edit and Singh, Jyoti and Wöckel, Simone and Farkas, Etelka and Meyer, Franc and Haukka, Matti and Nordlander, Ebbe}},
issn = {{1477-9234}},
language = {{eng}},
number = {{35}},
pages = {{8183--8194}},
publisher = {{Royal Society of Chemistry}},
series = {{Dalton Transactions}},
title = {{Unsymmetrical dizinc complexes as models for the active sites of phosphohydrolases.}},
url = {{http://dx.doi.org/10.1039/b925563j}},
doi = {{10.1039/b925563j}},
volume = {{39}},
year = {{2010}},
}