An ortho-palladated dimethylbenzylamine complex as a highly efficient turnover catalyst for the decomposition of P=S insecticides. Mechanistic studies of the methanolysis of some P=S-containing phosphorothioate triesters.

  title={An ortho-palladated dimethylbenzylamine complex as a highly efficient turnover catalyst for the decomposition of P=S insecticides. Mechanistic studies of the methanolysis of some P=S-containing phosphorothioate triesters.},
  author={Zhong-lin Lu and A. A. Neverov and R. Brown},
  journal={Organic \& biomolecular chemistry},
  volume={3 18},
An ortho-palladated complex Pd(dmba)(py)(OTf) (9), or Pd(N,N-dimethylbenzylamine)(pyridine)(trifluoromethanesulfonate), was synthesized and its solution properties in methanol studied as a function of pH. In neutral solution the triflate dissociates from the complex to give a dominant form Pd(dmba)(py)(HOCH3), and in acid the pyridine dissociates to give Pyr-H+ and Pd(dmba)(HOCH3)(HOCH3). Under basic conditions, Pd(dmba)(py)(HOCH3) ionizes to give Pd(dmba)(py)(-OCH3) from which the pyridine can… Expand
Palladacycle-promoted solvolytic cleavage of O,O-dimethyl O-aryl phosphorothioates. Converting a phosphorane-like transition state to an observable intermediate.
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Overall the best catalytic system is provided by equimolar Zn(2+), 5, and (-)OCH(3), which exhibits excellent turnover of the methanolysis of paraoxon when the substrate is in excess. Expand
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The Eu(3+)-promoted methanolysis of three esters, p-nitrophenyl acetate (1), phenyl acetate (2), and ethyl acetate (3) is reported, as well as the potentiometric titration of Eu(3+) in MeOH atExpand
Effect of steric hindrance on kinetic and equilibrium data for substitution reactions of diaqua(N-substituted ethylenediamine)palladium(II) with chloride in aqueous solution
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Hydrolysis of 4-nitro- and 2,4-dinitro-phenyl carboxylates proceeds catalytically in the presence of ortho-palladated aryl oximes 4. The catalytic reaction involves two active species, identified asExpand