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

Genoa R. Warner, Yogesh Somasundar, Cindy Weng, Mete H. Akin, Alexander D. Ryabov, Terrence J. Collins

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

Bis-sulfonamide bis-amide TAML activator [Fe{4-NO2C6H3-1,2-(NCOCMe2NSO2)2CHMe}] (2) catalyzes oxidative degradation of the oxidation-resistant neonicotinoid insecticide, imidacloprid (IMI), by H2O2 at pH 7 and 25 °C, whereas the tetrakis-amide TAML [Fe{4-NO2C6H3-1,2-(NCOCMe2NCO)2CF2}] (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]≪[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.

Original languageEnglish (US)
Pages (from-to)7631-7637
Number of pages7
JournalChemistry - A European Journal
Volume26
Issue number34
DOIs
StatePublished - Jun 18 2020
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Organic Chemistry

Keywords

  • TAML activators
  • environmental chemistry
  • kinetics
  • oxidation
  • reaction mechanism

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