RESUMO
The diMn(III) complexes [Mn2(5-Me-salpentO)(mu-MeO)(mu-AcO)(H2O)Br] (1) and [Mn2(3-Me-salpentO)(mu-MeO)(mu-AcO)(MeOH)2]Br (2), where salpentOH = 1,5-bis(salicylidenamino)pentan-3-ol, were synthesised and structurally characterized. The two complexes include a bis(micro-alkoxo)(micro-acetato) triply-bridged diMn(III) core with an Mn...Mn separation of 2.93-2.94 A, the structure of which is retained upon dissolution. Complexes 1 and 2 show catalytic activity toward disproportionation of H2O2, with first-order dependence on the catalyst, and saturation kinetics on [H2O2], in methanol and DMF. In DMF, the two complexes are able to disproportionate at least 1500 eq. of H2O2 without significant decomposition, while in methanol, they rapidly lose activity with formation of a non-coupled Mn(II) species. Electrospray ionisation mass spectrometry, EPR and UV/vis spectroscopy used to monitor the reaction suggest that the major active form of the catalyst occurs in the Mn2(III) oxidation state during cycling. The correlation between log(k(cat)) and the redox potentials of 1, 2 and analogous complexes of other X-salpentOH derivatives indicates that, in this series, the oxidation of the catalyst is probably the rate-limiting step in the catalytic cycle. It is also noted that formation of the catalyst-peroxide adduct is more sensitive to steric effects in DMF than in methanol. Overall, kinetics and spectroscopic studies of H2O2 dismutation by these complexes converge at a catalytic cycle that involves the Mn2(III) and Mn2(IV) oxidation states.
Assuntos
Catalase/química , Manganês/química , Compostos Organometálicos/química , Catálise , Cristalografia por Raios X , Eletroquímica , Cinética , Ligantes , Espectroscopia de Ressonância Magnética/métodos , Magnetismo , Modelos Moleculares , Estrutura Molecular , Compostos Organometálicos/síntese química , Sensibilidade e Especificidade , Espectrometria de Massas por Ionização por Electrospray/métodos , Espectrofotometria Infravermelho/métodos , Espectrofotometria Ultravioleta/métodosRESUMO
Two new diMn(III) complexes [Mn(2)(III)L(1)(mu-AcO)(mu-MeO)(methanol)(2)]Br (1) and [Mn(2)(III)L(2)(mu-AcO)(mu-MeO)(methanol)(ClO(4))] (2) (L(1)H(3)=1,5-bis(2-hydroxybenzophenylideneamino)pentan-3-ol; L(2)H(3)=1,5-bis(2-hydroxynaphtylideneamino)pentan-3-ol) were synthesized and structurally characterized. Structural studies evidence that these complexes have a bis(mu-alkoxo)(mu-carboxylato) triply bridged diMn(III) core in the solid state and in solution, with two substitution-labile sites--one on each Mn ion--in cis-position. The two complexes show catalytic activity toward disproportionation of H(2)O(2), with saturation kinetics on [H(2)O(2)], in methanol and dimethyl formamide at 25 degrees C. Spectroscopic monitoring of the H(2)O(2) disproportionation reaction suggests that (i) complexes 1 and 2 dismutate H(2)O(2) by a mechanism involving redox cycling between Mn(2)(III) and Mn(2)(IV), (ii) the complexes retain the dinuclearity during catalysis, (iii) the active form of the catalyst contains bound acetate, and (iv) protons favors the formation of inactive Mn(II) species. Comparison to other dimanganese complexes of the same family shows that the rate of catalase reaction is not critically dependent on the redox potential of the catalyst, that substitution of phenolate by naphtolate in the Schiff base ligand favors formation of the catalyst-substrate adduct, and that, in the non-protic solvent, the bulkier substituent at the imine proton position hampers the binding to the substrate.
Assuntos
Catalase/química , Peróxido de Hidrogênio/química , Compostos de Manganês/química , Manganês/química , Catalase/metabolismo , Química Inorgânica/métodos , Eletroquímica/métodos , Espectroscopia de Ressonância de Spin Eletrônica , Peróxido de Hidrogênio/metabolismo , Cinética , Ligantes , Espectroscopia de Ressonância Magnética , Magnetismo , Manganês/metabolismo , Compostos de Manganês/metabolismo , Metanol , Estrutura Molecular , Bases de Schiff , Espectrometria de Massas por Ionização por Electrospray , Espectrofotometria InfravermelhoRESUMO
The dimanganese(III,III) complexes [Mn(2)(III)(5-NO(2)-salpentO)(mu-AcO)(mu-MeO)(methanol)(2)]Y (1: Y=Br, 2a: Y=I, 2b: Y=I(3)), [Mn(2)(III)(5-NO(2)-salpentO)(mu-AcO)(mu-MeO)(methanol)(ClO(4))] (3) and [Mn(2)(III)(5-Cl-salpentO)(mu-AcO)(mu-MeO)(methanol)(2)]Br (4), where salpentOH is the symmetrical Schiff base ligand 1,5-bis(salicylidenamino)pentan-3-ol, were synthesised and structurally characterized. Complex 2b crystallises in the monoclinic system, space group P2(1)/c, and exhibits Mn. . .Mn separation of 2.911 A. This Mn. . .Mn separation is very close to the other characterized (mu-alkoxo)(2)(mu-acetato)Mn(2)(III) complexes of X-salpentOH (X=MeO, Br and H) and reveals that the aromatic substituent has little influence on the geometric parameters of the bimetallic core. A correlation between the electronic character of the different ring substituents, the redox potentials of the dinuclear complexes and their catalase activity was evidenced. Complexes 1-4 show saturation kinetics with [H(2)O(2)] and the H(2)O(2) disproportionation involves redox cycling between the Mn(2)(III)/Mn(2)(IV) levels. The catalytic activity studies show that bound acetate is required for catalase activity and that the acetato and alkoxo bridges serve as internal bases facilitating the proton transfer coupled to oxidation of the metal centre.