Zero-order Catalysis in TAML-catalyzed Oxidation of Imidacloprid, a Neonicotinoid Pesticide.

Bis-sulfonamide bis-amide TAML activator [Fe{4-NO2C6H3-1,2-(NCOCMe2NSO2)(2)CHMe}](-) (2) catalyzes oxidative degradation of the oxidation-resistant neonicotinoid insecticide, imidacloprid (IMI), by H2O2 at pH 7 and 25 degrees C, whereas the tetrakis-amide TAML [Fe{4-NO2C6H3-1,2-(NCOCMe2NCO)(2)CF2}](-) (1), previously regarded as the most catalytically active TAML, is inactive under the same conditions. At ultra-low concentrations of both imidacloprid and 2, 62 % of the insecticide was oxidized in 2 h, at which time the catalyst is inactivated; oxidation resumes on addition of a succeeding aliquot of 2. Acetate and oxamate were detected by ion chromatography, suggesting deep oxidation of imidacloprid. Explored at concentrations [2]>=[IMI], the reaction kinetics revealed unusually low kinetic order in 2 (0.164 +/- 0.006), which is observed alongside the first order in imidacloprid and an ascending hyperbolic dependence in [H2O2]. Actual independence of the reaction rate on the catalyst concentration is accounted for in terms of a reversible noncovalent binding between a substrate and a catalyst, which usually results in substrate inhibition when [catalyst]MUCH LESS-THAN[substrate] but explains the zero order in the catalyst when [2]>[IMI]. A plausible mechanism of the TAML-catalyzed oxidations of imidacloprid is briefly discussed. Similar zero-order catalysis is presented for the oxidation of 3-methyl-4-nitrophenol by H2O2, catalyzed by the TAML analogue of 1 without a NO2-group in the aromatic ring.