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Indian Journal of Chemistry -Section A (IJC-A) >
IJC-A Vol.49A [2010] >
IJC-A Vol.49A(03) [March 2010] >
| Title: | Oxidation of lower oxyacids of phosphorus by tetraethylammonium chlorochromate: A kinetic and mechanistic study |
| Authors: | Vadera, Khushboo
Sharma, D
Agarwal, S
Sharma, Pradeep K |
| Keywords: | Kinetics
Reaction mechanisms
Oxidations
Halochromates
Phosphorus acids |
| Issue Date: | Mar-2010 |
| Publisher: | CSIR |
| 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. |
| Page(s): | 302-306 |
| Source: | IJC-A Vol.49A(03) [March 2010]
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