Issue 8, 1987

Kinetic study of the homogeneous methanolysis of tetraphosphorus decasulphide

Abstract

The rate of the homogeneous methanolysis of pure P4S10, dissolved in CS2, has been measured at 0, 15, 25, and 35 °C for various MeOH:P4S10 molar ratios. The sole product detected was (MeO)2PS2H. At not too low concentrations, the reaction is virtually first order in [P4S10] and second order in [MeOH], owing probably to an autocatalytic process. The multistep reaction is kinetically controlled by the initial attack on P4S10; this is tentatively explained by the rigidity and geometry of the P4S10 cage molecule and/or by the spontaneous formation of reactive dithioxophosphoranes ZP([double bond, length half m-dash]S)2[Z = MeO– or > P(S)S–] from all alcoholysis intermediates. Calculated activation parameters are discussed. Novel data on the solubility of P4S10 are reported.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1987, 1897-1900

Kinetic study of the homogeneous methanolysis of tetraphosphorus decasulphide

P. Bourdauducq and M. C. Démarcq, J. Chem. Soc., Dalton Trans., 1987, 1897 DOI: 10.1039/DT9870001897

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