Dinuclear Zinc(II)−Iron(III) and Iron(II)−Iron(III) Complexes as Models for Purple Acid Phosphatases

Albedyhl, Sabine; Averbuch-Pouchot, Μ. Τ.; Belle, Catherine; Krebs, Bernt; Pierre, J.-L.; Saint‐Aman, Eric; Torelli, Stéphane

doi:10.1002/1099-0682(200106)2001:6<1457::aid-ejic1457>3.0.co;2-f

Cited by 83 publications

(79 citation statements)

References 33 publications

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“…Attempts to duplicate the catalytic, spectroscopic and mechanistic properties of phosphoesterases have been one of our goals, and the goals of many other workers in the area. [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] The metal ions of special interest in our own work (zinc(II), cobalt(II) and cadmium(II)) will be discussed. We acknowledge (i) the contributions of all previous authors upon which our contributions are built on, and (ii) the efforts of contemporary researchers in our area, whose work parallels ours.…”

Section: Dinuclear Metallohydrolasesmentioning

confidence: 99%

Spectroscopic and mechanistic studies of dinuclear metallohydrolases and their biomimetic complexes

et al. 2014

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An enhanced understanding of the metal ion binding and active site structural features of phosphoesterases such as the glycerophosphodiesterase from Enterobacter aerogenes (GpdQ), and the organophosphate degrading agent from Agrobacterium radiobacter (OpdA) have important consequences for potential applications. Coupled with investigations of the metalloenzymes, programs of study to synthesise and characterise model complexes based on these metalloenzymes can add to our understanding of structure and function of the enzymes themselves. This review summarises some of our work and illustrates the significance and contributions of model studies to knowledge in the area.

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Section: Dinuclear Metallohydrolasesmentioning

confidence: 99%

Spectroscopic and mechanistic studies of dinuclear metallohydrolases and their biomimetic complexes

et al. 2014

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“…Thus, FeZn complexes based on dinucleating ligands that contain a central bridging phenolate moiety have been published [9][10][11][12][13][14][15][16][17][18][19]. These model complexes have been prepared by simultaneous or stepwise addition of one equivalent of each metal salt.…”

Section: Introductionmentioning

confidence: 99%

Systematic synthesis of functional unsymmetric FeZn model complexes for plant purple acid phosphatases

Jarenmark

Carlsson

Трухан

et al. 2010

Inorganic Chemistry Communications

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a b s t r a c tThe heterodinuclear complexes [FeZn(L)(CH 3 CO 2 ) 2 ] + (L = ICIMP or IPCPMP) are structural models for the dinuclear active sites of plant purple acid phosphatases. They can be systematically synthesized from mononuclear iron complexes and enhance the rate of transesterification of 2-hydroxypropyl p-nitrophenyl phosphate, an assay for the catalytic hydrolysis performed by purple acid phosphatases.Ó 2009 Elsevier B.V. All rights reserved.The purple acid phosphatases catalyze the hydrolysis of phosphoesters at acidic pH. This class of enzymes contain active sites with dinuclear Fe(III)M(II) (M = Fe, Zn, Mn) cores [1], a number of which have been crystallographically characterized [2][3][4][5][6][7][8]. The structures of the active sites of the purple acid phosphatases isolated from plants are closely related and contain one iron and one zinc ion about 3.0-3.4 Å apart. The metals are ligated by histidines, tyrosines and carboxylate-containing amino acid residues and bridged by one of the carboxylate oxygens of an aspartate and a water or hydroxide molecule.The publication of the crystal structure of kidney bean purple acid phosphatase (kbPAP) [2] has provided impetus for the preparation of model complexes that may aid in the elucidation of the catalytic mechanism of this and related enzymes. Thus, FeZn complexes based on dinucleating ligands that contain a central bridging phenolate moiety have been published [9][10][11][12][13][14][15][16][17][18][19]. These model complexes have been prepared by simultaneous or stepwise addition of one equivalent of each metal salt. Here, we wish to present the controlled stepwise assembly of model complexes for kbPAP that not only contain an unsymmetric coordination environment, but also provide a vacant coordination site on one metal.The unsymmetric ligands H 2 ICIMP and H 2 IPCPMP (Fig. 1) have been shown to stabilize dinuclear species [20-22]. Addition of Fe (ClO 4 ) 3 (1-2 equivalents) to H 2 ICIMP in methanol, or FeCl 3 to an acetonitrile solution of H 4 IPCPMP(PF 6 ) 2 , yields purple solutions. The purple color indicates coordination of the phenolate moieties of the unsymmetric ligands; the color arises from the phenolate? Fe(III) LMCT electronic transition. Deep purple single crystals of the products [Fe(H 2 ICIMP)(H 2 O)Cl][Fe(H 2 ICIMP)(MeOH)Cl] [ClO 4 ] 4 (1) and [Fe(H 2 IPCPMP)Cl 2 ][PF 6 ] (2) [23] could be grown and their structures were determined by X-ray diffraction (Fig. 2) [24]. The structure of 1 contains two separate octahedrally coordinated Fe(ICIMP) molecules, which only differ in the bound solvent molecules (water or methanol). The iron(III) ion is in both cases located in the tetradentate pocket of the ligand, in keeping with the chelate effect. Another reason for the site preference may be the preference of the hard iron(III) ion for the hard carboxylate oxygen donor [25]. It is likely that the chloride ion originates from the ligand, which was isolated as a hydrochloride salt [26]. The crystal structure of 2 (Fig. 2, bottom) reveals an e...

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“…Mononuclear, [1][2] binuclear, [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] trinuclear, 17,18 tetranuclear [19][20][21][22][23] and polymeric 24 complexes have been reported in which the phosphate moieties adopt monodentate, chelating, and bridging binding modes. These examples include heterometallic complexes.…”

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“…37 In this complex, DMP is not bonded to the metal, and acts as a independent counter-ion. We have also reported the synthesis and crystal structures of [Fe 16 (µ 3 -O) 8 (µ 3 -OH) 4 (µ-OH) 4 (µ-DMP) 12 (µ-OAc) 12 -(DMSO)4]․2DMSO ․1.5H2O, 38 within which an macromolecule constellation consisting of sixteen iron ion connected by twelve bridging dimethyl phosphate, twelve bridging acetate, eight µ3-oxo, four µ3-OH, four µ-OH and four dimethyl sulfoxide ligands. We now report on the synthesis, characterization and crystal structure of novel polymer of praseodymium(III) and neodymium(III) complexes.…”

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confidence: 99%

Synthesis, Characterization, and Crystal Structures of Novel Coordination Polymers of Praseodymium(III) and Neodymium(III) Containing Dialkyl Phosphate

Rafizadeh¹,

Amani²,

Mortazavi³

2009

Bulletin of the Korean Chemical Society

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Metal complexes incorporating various types of phosphate moieties are being examined in order to explore the metalbinding properties of such ligands and to elucidate the importance of these interactions in biological systems. Mononuclear, 37 In this complex, DMP is not bonded to the metal, and acts as a independent counter-ion. We have also reported the synthesis and crystal structures of [Fe 16 38 within which an macromolecule constellation consisting of sixteen iron ion connected by twelve bridging dimethyl phosphate, twelve bridging acetate, eight µ3-oxo, four µ3-OH, four µ-OH and four dimethyl sulfoxide ligands. We now report on the synthesis, characterization and crystal structure of novel polymer of praseodymium(III) and neodymium(III) complexes. Experimental SectionAll chemicals were purchased from Merck and Aldrich. Infrared spectra (4000-250 cm -1 ) of solid samples were taken as 1% dispersion in KBr pellets using a Shimadzu-470 spectrometer. H NMR, 13C NMR and 31 P NMR spectra were acquired on a Bruker AC-300 MHz spectrometer at ambient temperature in D2O. Melting points were is uncorrected and were obtained by a Kofler Heizbank Rechart type 7841 melting point apparatus.Synthesis of [Nd(µ-DEP)3]n (1). Triethyl phosphate (3.31g, 3.1 mL, 18 mmol) was added to a solution of NdCl 3 (0.93 g, 3.6 mmol) in ethanol (40 mL) and DMSO (5mL) and the resulting pale violet solution was stirred at 40 °C for 30 minute. Then, it was left to evaporate slowly at room temperature. After two months, colorless prismatic crystals of 1 were isolated (yield 1.62 g, 74.56%, m.p < 300 o C). IR (KBr, ): 2984s, 2940m, 2912m (νCH), 1446w, 1399m, 1372w, 1197s, 1181s, 1168s, 1117s, 1093s, 1066s, 1044s (νC-O-P), 977s, 825s, 778m (νP-O), 576m, 541m, 504m, 409w, 388m, 332w (νNd-O

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Dinuclear Zinc(II)−Iron(III) and Iron(II)−Iron(III) Complexes as Models for Purple Acid Phosphatases

Cited by 83 publications

References 33 publications

Spectroscopic and mechanistic studies of dinuclear metallohydrolases and their biomimetic complexes

Spectroscopic and mechanistic studies of dinuclear metallohydrolases and their biomimetic complexes

Systematic synthesis of functional unsymmetric FeZn model complexes for plant purple acid phosphatases

Synthesis, Characterization, and Crystal Structures of Novel Coordination Polymers of Praseodymium(III) and Neodymium(III) Containing Dialkyl Phosphate

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