Addition reaction muonium, kinetics

The reactions of A-phenyl a-r-butyl nitrone (PEN) with maleimides, maleic anhydride, and diethyl maleate have been studied by EPR and two types of spin adduct detected. They arise from the reductive addition of PEN to the alkenes and the degradation product of DEN (2-methyl-2-nitropropane). The deuterium and muonium kinetic isotope effects for the addition of the hydrogen atom to a variety of alkenes have been determined experimentally and theoretically. ... 

Kinetic data for the reactions of diazodiphenylmethane in 10 different alcohols with 2-(4-phenyl substituted)cyclohex-l-enylcarboxylic acids (75) were correlated using the extended Hammett equation.68 Reaction of the species (76)-(78) with the light radioactive H isotope, the muonium atom, has been studied.69 The largest primary kinetic isotope effects ever reported (ca 850) are seen in this work for the addition of muonium to one of the C=0 groups. 

Muonium has been observed in pure hydrocarbons ( ), alcohols (, 7 ), and water ( ). Because Mu reacts slowly with these pure liquids, giving observable reaction lifetimes of Mu up to 4us, they can be used as solvents to study various solutes of interest. As the free triplet Mu atom reacts with the solute its observed precession frequency is damped and a decay constant, X can be obtained. The concentration dependence of the decay constant provides second order chemical rate constants for Mu addition, abstraction, spin conversion, and oxidation-reduction reactions. When analogous hydrogen atom rate constants are available the kinetic isotope effect can also be calculated. 

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