Reactions of carbenes at low temperatures. Diphenylcarbene and isobutene

Moss, Robert A.; Huselton, John K.

doi:10.1021/ja00472a059

Cited by 22 publications

(1 citation statement)

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“…Recently, another case in which equilibration of the two ends of an allylic radical was inhibited by a frozen matrix was reported. 80 The caged methyl-dimethylallyl radical pair from thermolysis of 2 (Table VI) undergoes recombination at the tail end of the delocalized radical 5.2 times as often as at the head end. This ratio agrees rather well with the value 5.7 obtained from the gas-phase photolysis of olefins81 and again speaks for the importance of steric factors in radical recombination.…”

Section: Discussionmentioning

confidence: 99%

Studies of the spin correlation effect in acyclic azo compounds

Engel¹,

Bishop²,

Page³

1978

J. Am. Chem. Soc.

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The direct and triplet-sensitized photolysis of two acyclic azoalkanes 1 and 2 has been examined in some detail. Whereas triplet sensitization usually leads to no reaction for acyclic azoalkanes, the triplet state of compounds 1 and 2 decomposes moderately efficiently without the intermediacy of the cis isomers. It was found that the cage effect for direct irradiation is much greater than that for sensitized decomposition. Although this result would normally be interpreted as a spin correlation effect (SCE), the difference is better explained as arising from stepwise decomposition of the azoalkane triplet state. The product distribution from 1 and 2 and the mechanism of azoalkane photolysis are discussed.

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Section: Discussionmentioning

confidence: 99%