Self‐ and cross‐disproportionation‐to‐combination rations for cyclopentyl and cyclohexyl radicals and their deuterated analogues

Abstract

Hydrogen, cycloalkene, and bicycloalkyl were found to be the principal products which account for ~9 7 % of all products formed in the gas-phase radiolysis of water vapor containing low concentrations of cycloalkanes. From the ratios of cycloalkene-to-bicycloalkyl yields extrapolated to the zero dose, the self-and cross-disproportionation-to-recombination rate constant ratios A

Disproportionation reactions between alkyl and fluoroalkyl radicals. II. Fluoro‐ and trifluoromethyl with ethyl radicals

“…The geometric mean rule assumes the steric factor relationship (P1.1 . PZ,Z)'/~ = PI,Z [36,37], and X, also depends upon the hard-sphere collision diameters that are assigned [37,38]. Experimental X, ratios involving alkyl and perfluoroalkyl radicals have frequently been reported in the range of 2.5-3.0 [38][39][40], such as CF3 + CH3 is 2.5 [39], CzFs + CZH5 is 3.2 [38].…”

Physicochemical Properties of Deuterated Compounds. 8th Communication. The kinetic isotope effect for the reaction of hydrogen atoms with methylcyclohexane and perdeuteromethylcyclohexane in the gas phase

“…Furthermore, the material balance expected from the reaction scheme, G(hydrogen) = G (cyclohexene) + G(bicyclohexyl), was confirmed [25] [26]. With methylcyclohexane, the radical R produced in Reactions 2 and 4 represents five isomeric radical species, i.e.…”

“…In the case where cyclohexane was taken as an additive, the main products were identified to be hydrogen, cyclohexene, and bicyclohexyl. Furthermore, the material balance expected from the reaction scheme, G(hydrogen) = G (cyclohexene) + G(bicyclohexyl), was confirmed [25] [26]. With methylcyclohexane, the radical R produced in Reactions 2 and 4 represents five isomeric radical species, i.e.…”

“…Materials. Triply distilled H20 was available from our previous works [21--23][25] [26]. Research-grade methylcyclohexane was obtained from Phillips Petroleum.…”

Mechanistic study of the Me2SiH–Me3Si radical system

“…The branching ratio relative to combination for reaction (14) is well known ;2,3 for reaction (11) we know that it is very small, k(11)/[k(4) ] k(5) ] k(11)] P 0.007,2 and nothing is known about the branching ratios of reactions ( 12) and (13).…”