title: Bioinspired FeIIICdII and FeIIIHgII complexes: synthesis, characterization and promiscuous catalytic activity evaluation.
abstract: In this work we report on the synthesis, crystal structure, and physicochemical characterization of the novel dinuclear [Fe(III)Cd(II)(L)(μ-OAc)(2)]ClO(4)·0.5H(2)O (1) complex containing the unsymmetrical ligand H(2)L=2-bis[{(2-pyridyl-methyl)-aminomethyl}-6-{(2-hydroxy-benzyl)-(2-pyridyl-methyl)}-aminomethyl]-4-methylphenol. Also, with this ligand, the tetranuclear [Fe(2)(III)Hg(2)(II)(L)(2)(OH)(2)](ClO(4))(2)·2CH(3)OH (2) and [Fe(III)Hg(II)(L)(μ-CO(3))Fe(III)Hg(II)(L)](ClO(4))(2)·H(2)O (3) complexes were synthesized and fully characterized. It is demonstrated that the precursor [Fe(III)(2)Hg(II)(2)(L)(2)(OH)(2)](ClO(4))(2)·2CH(3)OH (2) can be converted to (3) by the fixation of atmospheric CO(2) since the crystal structure of the tetranuclear organometallic complex [Fe(III)Hg(II)(L)(μ-CO(3))Fe(III)Hg(II)(L)](ClO(4))(2)·H(2)O (3) with an unprecedented {Fe(III)(μ-O(phenoxo))(2)(μ-CO(3))Fe(III)} core was obtained through X-ray crystallography. In the reaction 2→3 a nucleophilic attack of a Fe(III)-bound hydroxo group on the CO(2) molecule is proposed. In addition, it is also demonstrated that complex (3) can regenerate complex (2) in aqueous/MeOH/NaOH solution. Magnetochemical studies reveal that the Fe(III) centers in 3 are antiferromagnetically coupled (J=-7.2cm(-1)) and that the Fe(III)-OR-Fe(III) angle has no noticeable influence in the exchange coupling. Phosphatase-like activity studies in the hydrolysis of the model substrate bis(2,4-dinitrophenyl) phosphate (2,4-bdnpp) by 1 and 2 show Michaelis-Menten behavior with 1 being ~2.5 times more active than 2. In combination with k(H)/k(D) isotope effects, the kinetic studies suggest a mechanism in which a terminal Fe(III)-bound hydroxide is the hydrolysis-initiating nucleophilic catalyst for 1 and 2. Based on the crystal structures of 1 and 3, it is assumed that the relatively long Fe(III···)Hg(II) distance could be responsible for the lower catalytic effectiveness of 2.
authors: Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, Brazil.
authors: Fernando R
authors: FR
authors: Xavier
authors: Rosely A
authors: RA
authors: Peralta
authors: Adailton J
authors: AJ
authors: Bortoluzzi
authors: Valderes
authors: V
authors: Drago
authors: Eduardo E
authors: EE
authors: Castellano
authors: Wolfgang
authors: W
authors: Haase
authors: Zbigniew
authors: Z
authors: Tomkowicz
authors: Ademir
authors: A
authors: Neves
mesh_terms: D032701:Biomimetics; D002245:Carbon Dioxide / Q000737:chemistry; D002256:Carbonic Anhydrases / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D005290:Ferric Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D007501:Iron; D007700:Kinetics; D008628:Mercury; D008958:Models, Molecular; D008968:Molecular Conformation; D009941:Organomercury Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010755:Organophosphates / Q000737:chemistry*; D010744:Phosphoric Monoester Hydrolases / Q000138:chemical synthesis / Q000737:chemistry; D015204:Spectroscopy, Mossbauer
chemical_list: D005290:Ferric Compounds; D009941:Organomercury Compounds; D010755:Organophosphates; C546103:bis(2,4-dinitrophenyl) phosphate; D002245:Carbon Dioxide; D007501:Iron; D010744:Phosphoric Monoester Hydrolases; D002256:Carbonic Anhydrases; D008628:Mercury