Methidathion Complexes with Homoionic and Surfactant-Modified Montmorillonites

Abstract

The formation of the insecticide methidathion (S-[(5-methoxy-2-oxo-1,3,4-thiadiazol-3(2H)-yl)methyl] O,O-dimethyl phosphorodithioate) complexes with inorganic cation-saturated (Mg²⁺, Ca²⁺, Cu²⁺, and Ni²⁺) montmorillonites was investigated. The nature and structure of the complexes was determined by X-ray diffraction and infrared spectroscopy. The arrangement of the pesticide molecule in the interlayer space was also considered from ab initio calculations using simpler related molecules. The insecticide methidathion penetrated the interlayer spaces of the homoionic clay samples. The ligand–cation interactions in these complexes depend on the nature and characteristics of the saturating cations. Mechanisms involving water bridges and direct coordination with the exchange cation were proposed for the adsorption of methidathion by inorganic cation-saturated montmorillonites. The effect of the inorganic cations on the sorption of the cationic surfactant tetradecyltrimethylammonium bromide (TDTMA) by montmorillonite was also studied and the subsequent sorption of methidathion in TDTMA⁺-Montmorillonite determined. Van der Waals bonds constitute the methidathion adsorption mechanism by montmorillonite saturated with TDTMA⁺. The arrangements of methidathion and of the cationic surfactant molecules in the montmorillonite interlayer space were demostrated.