Abstract
Oxidation of three lower oxyacids of phosphorus, viz. phosphinic, phenylphosphinic and phosphorous acids by pyridinium hydrobromide perbromide (PHPB), is first-order with respect to both oxyacid and PHPB. There is no effect on addition of acylonitrile and pyridinium bromide. On oxidation, deuterated phosphinic and phosphorous acids exhibit substantial kinetic isotope effects. The effect of solvent composition on reaction rate indicates that the transition state is more polar than the reactants. Reaction rates were determined at different temperatures and the activation parameters calculated. Alternative mechanisms, involving the two tautomeric forms of the oxyacid, have been formulated and it has been concluded that the reaction proceeds through the pentacoordinated tautomer. Transfer of a hydride ion from the oxyacid to PHPB, in the rate-determining step, has been proposed.
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References
Asopa R, Mathur A and Banerji K K 1991Indian J. Chem. A30 784
Cowen H D, McCabe C L and Warner J C 1950J. Am. Chem. Soc. 72 1194
Djerassi C and Schloz C R 1948J. Am. Chem. Soc. 70 417
Falnberg A H and Winstein S 1956J. Am. Chem. Soc. 78 2770
Fieser L F and Fieser M 1967Reagents for organic synthesis (New York: John Wiley & Sons) vol. 1, p. 967
Fratiello A and Anderson E W 1963J. Am. Chem. Soc. 85 519
Gnanadoss L and Vijayalaxmi A 1980Indian J. Chem. B19 725
Gunn S R and Green L G 1961J. Phys. Chem. 65 779
Haight G P, Rose M and Preer J 1968J. Am. Chem. Soc. 90 4809
Heasley V L, Louie T J, Luttrull D K, Miller M D, Moore H B, Nogales D F, Sauerbrey A M, Shevel A B, Shibuya T Y, Stanley M S, Shellhamer D F and Heasley G E 1988J. Org. Chem. 53 2199
Jenkins W A and Yost D M 1959J. Inorg. Nucl. Chem. 11 297
Jones R T and Swift E S 1953Anal. Chem. 25 1271
Linehart G A and Adams E 1917J. Am. Chem. Soc. 39 948
Lovering E G and Laidler K J 1960Can. J. Chem. 38 2367
Mehrotra R N 1968J. Chem. Soc., Dalton Trans. 681
Mehrotra R N 1984J. Chem. Soc, Dalton Trans. 1531
Mehrotra R N 1985Can. J. Chem. 63 663
Mitchell A D 1923J. Chem. Soc. 2241
Moondra A, Mathur A and Banerji K K 1990aJ. Chem. Soc, Dalton Trans. 2967
Moondra A, Mathur A and Banerji K K 1990bIndian J. Chem. A29 963
Moondra A, Mathur A and Banerji K K 1991Int. J. Chem. Kinet. 23 1037
Nagori R R, Mehta M and Mehrotra R N 1979J. Chem. Soc, Perkin Trans. 2 216
Rajan S, Rajaram J and Kuriacose J C 1973Indian J. Chem. 11 1152
Sengupta K K and Chakladar J K 1973J. Chem. Soc, Perkin Trans. 2 929
Sengupta K K, Pal B B and Mukherjee D C 1974J. Chem. Soc., Dalton Trans. 226
Seth M, Mathur A and Banerji K K 1990Bull. Chem. Soc. Jpn. 63 3640
Sharma K and Mehrotra R N 1989Transition Met. Chem. 18 45
Van Wazer J R 1958Phosphorus and its compounds (New York: John Wiley & Sons) vol. 1
Vetter K J 1967Electrochemical kinetics, theoretical and experimental aspects (New York: Academic Press) p. 511
Viste A, Holm D A, Wong P L and Veith G D 1971Inorg. Chem. 10 631
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Varshney, S., Sharma, P.K. & Banerji, K.K. Kinetics and mechanism of oxidation of phosphorus oxyacids by pyridinium hydrobromide perbromide. Proc. Indian Acad. Sci. (Chem. Sci.) 104, 603–610 (1992). https://doi.org/10.1007/BF02843554
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DOI: https://doi.org/10.1007/BF02843554