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  • Title: Cu(II)-Mediated decomposition of phosphorothionate P=S pesticides. Billion-fold acceleration of the methanolysis of fenitrothion promoted by a simple Cu(II)-ligand system.
    Author: Neverov AA, Brown RS.
    Journal: Org Biomol Chem; 2004 Aug 07; 2(15):2245-8. PubMed ID: 15280962.
    Abstract:
    The kinetics of methanolysis of the title compound (3) were studied in the presence of Cu(2+), introduced as Cu(OTf), in the presence of 0.5-1.0 eq. of methoxide and in the presence of 1.0 eq. of a ligand such as bipyridyl (5), phenanthroline (6) or 1,5,9-triazacyclododecane (4). In all cases the active species involve Cu(2+)((-)OCH(3)). In the case of added strong-binding ligands 5 or 6, a plot of the observed rate constant for methanolysis of 3 vs. [Cu(2+)](total) gives a curved line modelled by a process having a [Cu(2+)](1/2) dependence consistent with an active monomeric species in equilibrium with an inactive dimer i.e.[LCu(2+)((-)OCH(3))](2) <==> 2LCu(2+)((-)OCH(3)). In the case of the added strong binding ligand 4, the plot of the observed rate constant for methanolysis of 3 vs.[Cu(2+)](total) gives a straight line consistent with the catalytically active species being Cu(2+)(OCH(3)) which shows no propensity to form inactive dimers. Turnover experiments where the [3] > [Cu(2+)](total) indicate that the systems are truly catalytic. In the optimum case a catalytic system comprising 1 mM of the complex 4Cu(2+)((-)OCH(3)) catalyzes the methanolysis of 3 with a t(1/2) of approximately 58 s accounting for a 1.7 x 10(9)-fold acceleration relative to the background reaction at near neutral (s)(s)pH (8.75).
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