title: Phosphoester hydrolysis: the incoming substrate turns the bridging hydroxido nucleophile into a terminal one.
abstract: Identifying the active nucleophile in hydrolysis reactions catalyzed by binuclear hydrolases is a recurrent problem and a matter of intense debate. We report on the phosphate ester hydrolysis by a Fe(III)Fe(II) complex of a binucleating ligand. This complex presents activities in the range of those observed for similar biomimetic compounds in the literature. The specific electronic properties of the Fe(III)Fe(II) complex allowed us to use (1)H NMR and Mössbauer spectroscopies to investigate the nature of the various species present in the solution in the pH range of 5-10. Both techniques showed that the hydrolysis activity is associated to a μ-hydroxido Fe(III)Fe(II) species. Further (1)H NMR experiments show that binding of anions or the substrate changes this bonding mode suggesting that a terminal hydroxide is the likely nucleophile in these hydrolysis reactions. This view is further supported by the structure determination of the hydrolysis product.
authors.affiliation: Univ. Grenoble Alpes, LCBM/PMB and CEA, IRTSV/CBM/PMB and CNRS, LCBM UMR 5249, PMB 38000 Grenoble (France).
authors.forename: Eric
authors.initials: E
authors.lastname: Gouré
authors.affiliation: Univ. Grenoble Alpes, LCBM/PMB and CEA, IRTSV/CBM/PMB and CNRS, LCBM UMR 5249, PMB 38000 Grenoble (France).
authors.forename: Michaël
authors.initials: M
authors.lastname: Carboni
authors.affiliation: Univ. Grenoble Alpes, LCBM/PMB and CEA, IRTSV/CBM/PMB and CNRS, LCBM UMR 5249, PMB 38000 Grenoble (France).
authors.forename: Angélique
authors.initials: A
authors.lastname: Troussier
authors.affiliation: Univ. Grenoble Alpes and CEA, INAC/SCIB/RICC, 38000 Grenoble (France).
authors.forename: Colette
authors.initials: C
authors.lastname: Lebrun
authors.affiliation: Univ. Grenoble Alpes and CEA, INAC/SCIB/RICC, 38000 Grenoble (France).
authors.forename: Jacques
authors.initials: J
authors.lastname: Pécaut
authors.affiliation: Univ. Grenoble Alpes and CEA, INAC/SCIB/RICC, 38000 Grenoble (France).
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Jacquot
authors.affiliation: Univ. Grenoble Alpes, LCBM/PMB and CEA, IRTSV/CBM/PMB and CNRS, LCBM UMR 5249, PMB 38000 Grenoble (France).
authors.forename: Patrick
authors.initials: P
authors.lastname: Dubourdeaux
authors.affiliation: Univ. Grenoble Alpes, LCBM/PMB and CEA, IRTSV/CBM/PMB and CNRS, LCBM UMR 5249, PMB 38000 Grenoble (France).
authors.forename: Martin
authors.initials: M
authors.lastname: Clémancey
authors.affiliation: Univ. Grenoble Alpes, LCBM/PMB and CEA, IRTSV/CBM/PMB and CNRS, LCBM UMR 5249, PMB 38000 Grenoble (France).
authors.forename: Geneviève
authors.initials: G
authors.lastname: Blondin
authors.affiliation: Univ. Grenoble Alpes, LCBM/PMB and CEA, IRTSV/CBM/PMB and CNRS, LCBM UMR 5249, PMB 38000 Grenoble (France). jean-marc.latour@cea.fr.
authors.forename: Jean-Marc
authors.initials: JM
authors.lastname: Latour
mesh_terms: D019297:2,4-Dinitrophenol / Q000031:analogs & derivatives* / Q000737:chemistry; D005290:Ferric Compounds / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D006878:Hydroxides / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D010755:Organophosphates / Q000737:chemistry*; D015204:Spectroscopy, Mossbauer
chemical_list: D005290:Ferric Compounds; D005296:Ferrous Compounds; D006878:Hydroxides; D010755:Organophosphates; C047468:2,4-dinitrophenylphosphate; D019297:2,4-Dinitrophenol
keywords: Mössbauer spectroscopy; NMR spectroscopy; binuclear hydrolases; diiron centers; phosphate esters