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Effects of ring strain on gas‐phase rate constants. 3. NO 3 radical reactions with cycloalkenes
Author(s) -
Atkinson Roger,
Aschmann Sara M.,
Long William D.,
Winer Arthur M.
Publication year - 1985
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550170904
Subject(s) - chemistry , cycloheptene , cyclopentene , cyclohexene , reaction rate constant , bicyclic molecule , radical , methylcyclohexane , double bond , heptene , ring strain , alkene , medicinal chemistry , computational chemistry , molecule , organic chemistry , kinetics , catalysis , quantum mechanics , physics
Rate constants for the gas‐phase reactions of NO 3 radicals with a series of cycloalkenes have been determined at 298 ± 2 K, using a relative rate technique. Using an equilibrium constant for the NO 2 + NO 3 ⇄ N 2 O 5 reactions of 3.4 × 10 −11 cm 3 molecule −1 , the following rate constants (in units of 10 −13 cm 3 molecule −1 s −1 ) were obtained: cyclopentene, 4.52 ± 0.52; cycloheptene, 4.71 ± 0.56; bicyclo[2.2.1]‐2‐heptene, 2.41 ± 0.28; bicyclo[2.2.2]‐2‐octene, 1.41 ± 0.17; bicyclo[2.2.1]‐2,5‐heptadiene, 9.92 ± 1.13; and 1,3,5‐cycloheptatriene, 12.6 ± 2.9. When combined with previous literature rate constants for cyclohexene and 1,4‐cyclohexadiene, these data show that the rate constants for the nonconjugated cycloalkenes studied depend to a first approximation on the number of double bonds and the degree and configuration of substitution per double bond. No obvious effects of ring strain energy on these NO 3 radical addition rate constants were observed. Our previous a priori predictive techniques for the alkenes and cycloalkenes can now be extended to strained cycloalkenes.