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Theoretical models for the reduction of arylmethyl halides by triorganotin hydrides
Author(s) -
Mahiou Belaid,
Clapp Gary E.,
Gleicher Gerald J.,
Freeman Peter K.,
Camaioni Donald M.
Publication year - 1991
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610040804
Subject(s) - chemistry , halogen , radical , electron transfer , chlorine , halide , bromine , nitrogen atom , photochemistry , computational chemistry , medicinal chemistry , ring (chemistry) , organic chemistry , alkyl
Two mechanistic pathways have been proposed for halogen atom transfer from the benzylic positions of halomethylarenes to triorganotin radicals. These are direct atom abstraction, which might involve an extremely polar transition state, and single electron transfer followed by bond cleavage. AM1 semi‐empirical calculations have been utilized to model the rate‐determining step of these processes. A wide range of related families of compounds have been studied, including substituted halomethylbenzes, selected halomethyl‐substituted polycyclic aromatic hydrocarbons and oxygen‐ and nitrogen‐containing chloromethyl‐substituted heteroaromatic systems. Although these calculations are relatively simple, the present results corroborate the view that chlorine and bromine atom transfer from the benzylic position to triorganotin radicals involves a direct atom abstraction in the rate‐determining step whereas reduction of the corresponding iodides proceeds via an electron‐transfer mechanism.