Abstract
The rates of oxidation of 3,5-di-tert-butyl catechol (3,5-DTBC) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ) by atmospheric dioxygen in the presence of five nickel(II)-polyoximate complexes as catalysts were measured at five different substrate-to-catalyst ratios. In all cases, saturation kinetics were observed at high substrate concentration. Analysis of the data using the Michaelis Menten model reveals rate constant values (kcat) ranging from 120 to 400h−1, which are comparable to results for other Ni(II)-polyoximate complexes in the literature. For the set of five catalysts examined in this work, those with the fewer number of coordinating groups on their polyoximate ligands showed the highest rates of reaction, while those with the higher number of coordinating groups showed the lowest rates of reaction. These results suggest that greater flexibility and possibly lower hindrance in the coordination sphere of the nickel centers of the catalysts enhance the rate of catalysis.
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