Abstract
The decomposition of [(NMe2)2CSNO]+ to [(NMe2)2CSSC(NMe2)2]2++ 2NO˙ has been investigated spectrophotometrically using the method of initial rates. The thionitrite was generated by mixing deoxygenated solutions of tetramethylthiourea and nitrous acid in a stopped-flow apparatus. For reaction with a large excess of tetramethylthiourea over nitrous acid the observed rate law (below) was similar to that reported for the analogous thiourea system. In solutions initially saturated with NO˙ν0=k1[(NMe2)2CSNO+][(NMe2)2CS]+k2[(NMe2)2CSNO+]2 the first term is largely suppressed. For systems in which [(NMe2)2CSNO]+ or [(NH2)2CSNO]+ was generated quantitatively from (NMe2)2CS or (NH2)2CS by reaction with a large excess of HNO2 the first term is again suppressed, but a new term in the rate law involving catalysis by nitrous acid occurs. The mechanisms of the decomposition reactions are discussed.
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