Zero-Order Catalysis in TAML-Catalyzed Oxidation of Imidacloprid, a Neonicotinoid Pesticide.

Bis-sulfonamide bis-amide TAML activator [Fe{4-NO2 C6 H3 -1,2-(NCOCMe2 NSO2 )2 CHMe}]- (2) catalyzes oxidative degradation of the oxidation-resistant neonicotinoid insecticide, imidacloprid (IMI), by H2 O2 at pH 7 and 25 °C, whereas the tetrakis-amide TAML [Fe{4-NO2 C6 H3 -1,2-(NCOCMe2 NCO)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 [H2 O2 ]. 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]≪[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 H2 O2 , catalyzed by the TAML analogue of 1 without a NO2 -group in the aromatic ring.