ABSTRACT
Methanesulfonyl iodide is produced in aqueous solutions from the reaction of triiodide with methanesulfinate. Dichroic crystals of (CH3SO2I)4·KI3·2I2 are formed from KI/I2 solutions with high concentrations of CH3SO2-, while dichroic crystals of (CH3SO2I)2·RbI3 are formed from RbI/I2 solutions. X-ray crystallography of these two compounds shows that the CH3SO2I molecules coordinate through their oxygen atoms to the metal cations and that the S-I bond length is 2.44 Å. At low concentrations of CH3SO2-, the solutions remain homogeneous and the sulfonyl iodide is formed in a rapid equilibrium: CH3SO2- + I3- â CH3SO2I + 2I-, KMSI = 1.07 ± 0.01 M at 25 °C (µ = 0.1 M, NaClO4). The sulfonyl iodide solutions display an absorbance maximum at 309 nm with a molar absorptivity of 667 M-1 cm-1. Stopped-flow studies reveal that the equilibrium is established within the dead time of the instrument (â¼2 ms). Solutions of CH3SO2I decompose slowly to form the sulfonate: CH3SO2I + H2O â CH3SO3- + I- + 2H+, khyd. In dilute phosphate buffer, this decomposition occurs with khyd = 2.0 × 10-4 s-1; the decomposition rate shows an inverse-squared dependence on [I-] because of the KMSI equilibrium.
