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Unsymmetrical dizinc complexes as models for the active sites of phosphohydrolases.

Jarenmark, Martin LU ; Csapó, Edit; Singh, Jyoti LU ; Wöckel, Simone; Farkas, Etelka; Meyer, Franc; Haukka, Matti and Nordlander, Ebbe LU (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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author
organization
publishing date
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
ISSN
1477-9234
DOI
10.1039/b925563j
language
English
LU publication?
yes
id
7c60f491-c019-4524-8af3-948884fab281 (old id 1665608)
date added to LUP
2010-09-10 14:10:58
date last changed
2018-05-29 09:45:21
@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},
  volume       = {39},
  year         = {2010},
}