Unsymmetrical dizinc complexes as models for the active sites of phosphohydrolases

Martin Jarenmark, Edit Csapó, Jyoti Singh, Simone Wöckel, E. Farkas, Franc Meyer, Matti Haukka, Ebbe Nordlander

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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 H4IPCPMP(PF6)2· 2H2O (H4L), which has been structurally characterized, and has been used to form two different Zn(ii) complexes, [{Zn2(IPCPMP) (OAc)}2][PF6]2 (2) and [{Zn2(IPCPMP) (Piv)}2][PF6]2 (3) (OAc = acetate; Piv = pivalate). The crystal structures of 2 and 3 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 2, 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.

Original languageEnglish
Pages (from-to)8183-8194
Number of pages12
JournalDalton Transactions
Volume39
Issue number35
DOIs
Publication statusPublished - Sep 21 2010

Fingerprint

Phosphoric Monoester Hydrolases
Hydroxides
Deprotonation
Nucleophiles
Transesterification
Mass spectrometry
Infrared spectroscopy
Hydrolysis
Acetates
Salts
Crystal structure
Ligands
Molecules
Kinetics
Water
bis(2,4-dinitrophenyl) phosphate
4-cresol
2-(hydroxypropyl)-4-nitrophenyl phosphate

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Jarenmark, M., Csapó, E., Singh, J., Wöckel, S., Farkas, E., Meyer, F., ... Nordlander, E. (2010). Unsymmetrical dizinc complexes as models for the active sites of phosphohydrolases. Dalton Transactions, 39(35), 8183-8194. https://doi.org/10.1039/b925563j

Unsymmetrical dizinc complexes as models for the active sites of phosphohydrolases. / Jarenmark, Martin; Csapó, Edit; Singh, Jyoti; Wöckel, Simone; Farkas, E.; Meyer, Franc; Haukka, Matti; Nordlander, Ebbe.

In: Dalton Transactions, Vol. 39, No. 35, 21.09.2010, p. 8183-8194.

Research output: Contribution to journalArticle

Jarenmark, M, Csapó, E, Singh, J, Wöckel, S, Farkas, E, Meyer, F, Haukka, M & Nordlander, E 2010, 'Unsymmetrical dizinc complexes as models for the active sites of phosphohydrolases', Dalton Transactions, vol. 39, no. 35, pp. 8183-8194. https://doi.org/10.1039/b925563j
Jarenmark, Martin ; Csapó, Edit ; Singh, Jyoti ; Wöckel, Simone ; Farkas, E. ; Meyer, Franc ; Haukka, Matti ; Nordlander, Ebbe. / Unsymmetrical dizinc complexes as models for the active sites of phosphohydrolases. In: Dalton Transactions. 2010 ; Vol. 39, No. 35. pp. 8183-8194.
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