Some Organic Reactions Involving the Occurence of Free Radicals in Solution.

A Brief History of Carbon Radicals

“…20 At about the same time, Kharasch proposed the now well-accepted mechanism for anti-Markovnikov addition of HBr to alkenes in the presence of peroxides, 21 a reaction he had initially reported with Mayo 4 years earlier. 22 Also in 1937 came Flory's definitive paper on the kinetics of vinyl polymerization reactions, confirming the nature of these reactions as free radical propagations.…”

Diaminoarylnickel(II) “Pincer” Complexes: Mechanistic Considerations in the Kharasch Addition Reaction, Controlled Polymerization, and Dendrimeric Transition Metal Catalysts

“…We feel that coordination of an alkene is not the first stage of the catalytic cycle. The addition of CCl 4 to a mixture of [Ni(NCN)Br] in dichloromethane in the absence of alkene leads to the formation of CBrCl 3 . This confirms that the interaction of the Ni-Br bond with the polyhalogenated alkane is an important fundamental feature (cf., Scheme 2) and that this step is reversible (hence, the saturation kinetic behavior).…”

Modulation spectroscopy: A technique for the study of free radicals in solution

“…Homolytic aromatic substitution has been the subject of extensive investigation for almost five decades [24,25]. To some extent, the description of the reaction as a substitution process is a misnomer, since the mechanism involves addition of a radical R. to benzene.…”