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Photochemical Generation and Structure of Vinyl Radicals (Eur. J. Org. Chem. 3/2008)
Author(s) -
Goumans Theodorus P. M.,
van Alem Kaj,
Lodder Gerrit
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200890000
Subject(s) - chemistry , radical , photodissociation , halide , photochemistry , intramolecular force , bent molecular geometry , organic chemistry
Abstract The cover picture shows how the structure of an α‐CN vinyl radical is elucidated through the photolysis of stereoisomeric vinyl halide precursors. The vinyl radical intermediates react with the solvent to form stereoisomeric styrenes. Analysis of the yields of the styrenes as a function of temperature establishes the α‐CN vinyl radical as a rapidly inverting bent, and not linear, species. The photolyses of α‐Me, α‐C(H)=O and α‐F substituted bromostyrenes indicate that the α‐Me vinyl radical is also rapidly inverting, while the α‐C(H)=O and α‐F vinyl radicals are stable bent species. The experimental results are supported by quantum chemical computations. Details are discussed in the article by T. P. M. Goumans et al. on p. 435 ff. Patty Nieuwenburg is acknowledged for the background photo of the dunes of Harlech, Wales.