ZnIIFeIII and FeIIFeIII Complexes Containing a Novel (μ‐Phenoxo)bis(μ‐diphenylphosphato)‐dimetal(<scp>II,III</scp>) Core as Model Complexes for Active Sites of Purple Phosphatases

Schepers, K.; Bremer, Bernd; Krebs, Bernt; Henkel, Gerald; Althaus, Erika; Mosel, Bernd D.; Müller‐Warmuth, W.

doi:10.1002/anie.199005311

Cited by 57 publications

(36 citation statements)

References 17 publications

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“…This causes a considerable elongation of the Zn-O1 distance and also leads to an increase in the Fe-Zn distance to 3.4556(6) Å compared to 3.3392(6) Å for 3. The intermetal distances in both complexes are slightly longer than the distances determined for kbPAP, but that of 3 is 0.1-0.2 Å shorter than those observed for previously published FeZn complexes of this type [11][12][13][14]16,18], except a l-OH-bridged complex [17]. For all complexes in this study the imidazolyl-metal bonds are shorter than the corresponding pyridyl-metal bonds.…”

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confidence: 63%

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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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confidence: 63%

“…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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“…The Zn ··· Fe distance of 3.7402(7) Å is slightly longer than in other complexes where the metals are linked by three bridges, one phenoxy and two μ‐diphenylphosphate groups. In [ZnFe(BPMP){O 2 P(OPh) 2 } 2 ] 2+ and [ZnFe(BPMOP){O 2 P(OPh) 2 } 2 ] 2+ the intermetallic distances are 3.695(1) Å3 and 3.7030(7) Å,5 respectively.…”

Section: Resultsmentioning

confidence: 99%

“…Although the metal ions in KBPAP are in two chemically distinct environments, the heterodinuclear Zn II Fe III complexes described as models for the active site of KBPAP3−8 have been prepared from symmetrical ligands. Only limited examples of unsymmetrical Zn II Fe III complexes have been reported.…”

Section: Introductionmentioning

confidence: 99%

Regio-Directed Synthesis of a ZnIIFeIII Complex from an Unsymmetrical Ligand and Its Relevance to Purple Acid Phosphatases

Belle

Gautier‐Luneau

Karmazin

et al. 2002

Eur. J. Inorg. Chem.

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A new heterodinuclear Zn II Fe III µ-phenoxy complex has been prepared and isolated from the unsymmetrical ligand 2-{[bis(2-hydroxybenzyl)]amino}methyl-6-{[2-pyridinylmethyl)amino]methyl}-4-methylphenol (H 3 L 1 ), which provides two distinct N-and O-rich donor sets. The regioselective complexation is confirmed in solution by 1 H NMR studies (comparison of the spectra obtained from H 3 L 1 and HL 2 − a ligand with only the N-donor set available − and a zinc salt).

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“…Among others, phenolate-, alkoxo-, and imidazolate have been deployed as scaffolds for a range of ligands varying in the aminomethyl-substituents (depicted as R x in Chart 3) in order to tune the coordination behavior of the ligands towards specific metal ions. 81,[90][91][92][93][94][95][96][97][98][99] The phenolate-linker is one of the most commonly used ligand scaffolds, 90,[92][93][94][95][96]99 for example in the symmetric ligands HL 1 and H3L 3 (see Chart 4). 100,101 (The nomenclature of the ligands denotes the number of protons which can potentially be abstracted from the ligands upon deprotonation; HL 1 contains one potentially acidic phenolate residue, accordingly HL 1 , while H3L 3 bears three acidic protons and the nomenclature is adjusted accordingly.…”

Section: Introductionmentioning

confidence: 99%

The impact of the second coordination sphere in phosphatase model complexes

Bosch¹

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Zn^IIFe^III and Fe^IIFe^III Complexes Containing a Novel (μ‐Phenoxo)bis(μ‐diphenylphosphato)‐dimetal(II,III) Core as Model Complexes for Active Sites of Purple Phosphatases

Cited by 57 publications

References 17 publications

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

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

Regio-Directed Synthesis of a ZnIIFeIII Complex from an Unsymmetrical Ligand and Its Relevance to Purple Acid Phosphatases

The impact of the second coordination sphere in phosphatase model complexes

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ZnIIFeIII and FeIIFeIII Complexes Containing a Novel (μ‐Phenoxo)bis(μ‐diphenylphosphato)‐dimetal(II,III) Core as Model Complexes for Active Sites of Purple Phosphatases

Cited by 57 publications

References 17 publications

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

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

Regio-Directed Synthesis of a ZnIIFeIII Complex from an Unsymmetrical Ligand and Its Relevance to Purple Acid Phosphatases

The impact of the second coordination sphere in phosphatase model complexes

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Zn^IIFe^III and Fe^IIFe^III Complexes Containing a Novel (μ‐Phenoxo)bis(μ‐diphenylphosphato)‐dimetal(II,III) Core as Model Complexes for Active Sites of Purple Phosphatases