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Factors controlling the addition of carbon‐centered radicals to alkenes
Author(s) -
Fischer Hanns,
Radom Leo
Publication year - 2002
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/1521-3900(200206)182:1<1::aid-masy1>3.0.co;2-s
Subject(s) - radical , steric effects , substituent , reaction rate constant , chemistry , polar , computational chemistry , ab initio quantum chemistry methods , ab initio , thermodynamics , photochemistry , organic chemistry , molecule , kinetics , physics , quantum mechanics , astronomy
Abstract The addition rate constants of radicals to alkenes are strongly substituent dependent because of enthalpic, polar and steric effects. Recent absolute experimental and high level ab initio data for many prototype additions of small radicals are analyzed with the aid of the state correlation diagram. This leads to a unifying rationalization of the various effects and allows the prediction of rate constants to one order of magnitude or better. Propagation rate coefficients of homo‐ and copolymerizations and penultimate effects are also discussed.