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|Title:||Oxidation of lower oxyacids of phosphorus by tetraethylammonium chlorochromate: A kinetic and mechanistic study|
Sharma, Pradeep K
|Keywords:||Kinetics;Reaction mechanisms;Oxidations;Halochromates;Phosphorus acids|
|IPC Code:||Int. Cl.9 CO7B33/00|
|Abstract:||Oxidation of lower oxyacids of phosphorus by tetraethylammonium chlorochromate in dimethyl sulphoxide leads to the formation of corresponding oxyacids with phosphorus in a higher oxidation state. The reaction exhibits 1:1 stoichiometry. The reaction is first order each with respect to chlorochromate and the oxyacids. The reaction does not induce polymerization of acrylonitrile. The oxidation of deuterated phosphinic and phosphorous acids exhibits a substantial primary kinetic isotope effect. The oxidation has been studied in nineteen different organic solvents. The effect of solvent indicates that the solvent polarity plays a major role in the process. It has been shown that the pentacoordinated tautomer of the phosphorus oxyacid is the reactive reductant and the tricoordinated form of phosphorus oxyacids does not participate in the oxidation process. A mechanism involving transfer of a hydride ion in the rate determining step has been proposed.|
|Appears in Collections:||IJC-A Vol.49A(03) [March 2010]|
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