Organic Peroxides. III. The Behavior of Cyclohexaneformyl Peroxide in the Presence of Excess Stable Radicals. The Simultaneous Determination of Kinetics and Free Radical Efficiencies in the Thermal Decompositions of Free Radical Initiators

Solvent Cage Effects in Organocobalt Corrinoid Chemistry: Thermal Homolysis of α- and β-(Cyanomethyl)cobinamides1

“…Solvent cage effects have long been recognized as being important in organic chemistry, − but the importance of such effects in the measurement of organometallic bond cleavage energetics was only recognized fairly recently. − Koenig and Finke 10,11 have provided the formalism needed to treat such cage effects in organometallic bond dissociation reactions exactly (eq 1) In the presence of a kinetically competent trap for one or both of the free radical products (which prevents reentry of the product radicals into the cage), application of the steady-state approximation to the concentration of the caged pair leads to eq 2…”

Thermal decomposition of organic oxalates, tritylazocarboxylates, and triphenylacetates

“…The alkylcarboxy radical (RCO-), a close relative of the alkoxy carbonyl radical, is thought to be generated by the thermal decomposition of diacyl peroxides. Thermal decomposition had usually been considered to proceed by initial hotnolytic cleavage (28,29,33,39,45,47,54,57,58,89) of the 0-0 bond and/or direct conversion of peroxide to ester which is frequently a major product by trapping the carboxy radi Another approach to the generation of the carboxy radical is through the thermal decomposition of ^-butylperoxy esters. Using iodine as a radical trap homolytic decomposition of t-butylperoxy phenylacetate has been shown to be entirely concerted (13); essentially no carboxy radical could be trapped.…”

Thermal decomposition of organic oxalates, tritylazocarboxylates, and triphenylacetates

“…The alkylcarboxy radical (RCO-), a close relative of the alkoxy carbonyl radical, is thought to be generated by the thermal decomposition of diacyl peroxides. Thermal decomposition had usually been considered to proceed by initial hotnolytic cleavage (28,29,33,39,45,47,54,57,58,89) of the 0-0 bond and/or direct conversion of peroxide to ester which is frequently a major product by trapping the carboxy radi cal. Recent publications by Taylor and Martin (85,86) carboxy-inversion process on the route to methyl acetate (86).…”