Premium
The Origin of the Remarkable Regioselectivity of Fe + ‐Mediated Dehydrogenation in Benzocycloalkenes
Author(s) -
Hertwig Roland H.,
Seemeyer Katrin,
Schwarz Helmut,
Koch Wolfram
Publication year - 1997
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19970030819
Subject(s) - regioselectivity , dehydrogenation , chemistry , ring (chemistry) , density functional theory , octene , computational chemistry , heptene , stereochemistry , organic chemistry , bicyclic molecule , catalysis , ethylene
Combined mass spectrometric experiments and density functional theory (DFT) calculations have been performed to determine the regioselectivity and uncover the origin of the CH bond activation of benzocycloalkenes by “bare” Fe I cations. The hydrocarbons investigated are benzocyclohexene, ‐heptene, and ‐octene. Extensive labeling experiments demonstrate that the site of CH bond activation in the non‐aromatic ring is dependent on the ring size. The barriers for the dehydrogenation process as predicted by DFT calculations are in agreement with the experimental findings. Further, the combined experimental and theoretical approach applied in the present study allows the principles underlying the remarkable ring size dependent regioselectivity of CH bond activation in these hydrocarbons to be unraveled.