ABSTRACT
The possibility of monooxygenase enzymes biomimetic construction models with the use of polynuclear manganese complexes was shown. It was demonstration that benzene is oxidized by polynuclear manganese complex [Mn12O12(CH3CO2)16(H2O)4] in acetonitrile solution at room temperature and atmospheric pressure yielding phenol with the selectivity more than 80%. It was determined that the addition of air oxygen as the reoxidizer to the reaction mixture didn't transfer the reaction into the catalytic mode.
Subject(s)
Benzene/chemistry , Manganese Compounds/chemistry , Catalysis , Molecular Mimicry , Oxidation-Reduction , TemperatureABSTRACT
Three new nickel(II) complexes with ligands 1,8-bis(2'-pyridyl)-3,6-dithiaoctane (Pdto) and dithiosemicarbazone of 4,7-dithiadecane-2,9-dione (DtdtzH2) of composition Ni(Pdto)(H2O)2(ClO4)2, Ni(DtdtzH2)(ClO4)2 and Ni(Dtdtz) were prepared, their molecular structures, spectral and redox-properties were studied. The possibilities of chemical reduction of Ni(Pdto)(H2O)2(ClO4)2 to nickel(I) and nickel(0) species and the reaction of nickel(I) complex with CO were shown, which may be described as the modeling of one of the stages of reactions with CO on active Ni-Fe-site of Ni-CO-dehydrogenases. It was found that Ni(DtdtzH2)(ClO4)2 reacted with (Et4N)2[Fe4S4(SBz)4] (BzSH = C6H5 CH2SH) forming adduct. In the row of studied complexes Ni(Pdto) (H2O)2(ClO4)2 may be described as the best structural model of Ni-Fe-site of Ni-CO-dehydrogenases on the redox properties.
