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Intermediate ion–neutral complexes formed during the gas‐phase protonolysis of p ‐( tert ‐butyl)‐substituted α,ω‐diphenylalkanes
Author(s) -
Matthias Carsten,
Kuck Dietmar
Publication year - 1993
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210281016
Subject(s) - chemistry , isobutane , protonation , hydride , medicinal chemistry , methylene , steric effects , kinetic isotope effect , ion , deuterium , photochemistry , hydrogen , stereochemistry , organic chemistry , quantum mechanics , physics , catalysis
Loss of isobutane is the exclusive fragmentation channel of long‐lived protonated tert ‐butyl‐substituted α,ω‐diphenylalkanes with chain lengths n = 2–12. Methane chemical ionization/mass‐analysed ion kinetic energy spectrometry of the [M + H] + ions and several deuterium‐labelled tert ‐butyl‐substituted 1,2‐, 1,3‐ and 1,10‐diphenylalkanes revealed that the reaction involves with equal probability and maximum regioselectivity a hydride ion from both the adjacent and the remote benzylic methylene groups, irrespective of the length of the aliphatic chain. The isotope effect of the hydride abstraction step was found to be same in all cases, k [C 4 H 10 ]/ k [C 4 H 9 D] = 1.6 ± 0.1. A sterically restricted system, protonated 1‐benzyl‐4‐( tert ‐butylbenzyl)benzene, shows the same behaviour. This implies, as a general phenomenon, the formation of intermediate ion–neutral complexes [C 4 H 9 + Ar(CH 2 ) n Ar] along with (or instead of) the corresponding π complexes [C 4 H 9 + … Ar(CH 2 ) n Ar] prior to isobutane elimination (Ar represents a phenyl or substituted‐phenyl group).