Premium
Polar Addition of Hydrogen Halides onto Olefins
Author(s) -
Dewar J. S.,
Fahey R. C.
Publication year - 1964
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.196402451
Subject(s) - carbonium ion , electrophile , chemistry , halide , ion , polar , photochemistry , computational chemistry , inorganic chemistry , organic chemistry , catalysis , physics , quantum mechanics
Various structures have been proposed for the intermediates of electrophilic additions onto olefins; these include halonium ions, classical carbonium ions, π‐complexes (i.e. nonclassical carbonium ions), and π‐complexes with back‐coordination. It is shown here that it is impossible to use any one of these entities alone to explain all such electrophilic additions; the electrophile itself determines the nature of the transition state formed. Polar addition of hydrogen halides onto olefins appears to proceed via a classical carbonium ion which does not occur as the free ion but as an undissociated ion pair. Various other mechanisms have been excluded by studies reported here of the stereochemical course of such additions.