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Substituent Effects on the Bond‐Dissociation Energies of Cationic Arene−Transition‐Metal Complexes
Author(s) -
Schroeter Katrin,
Wesendrup Ralf,
Schwarz Helmut
Publication year - 1998
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/(sici)1099-0690(199804)1998:4<565::aid-ejoc565>3.0.co;2-j
Subject(s) - chemistry , substituent , bond dissociation energy , dissociation (chemistry) , halogen , benzene , cationic polymerization , transition metal , alkyl , medicinal chemistry , metal , computational chemistry , stereochemistry , photochemistry , organic chemistry , catalysis
The bond‐dissociation energies ( BDE s) of more than twenty arene−M + complexes (M = Cr, Fe, Co) have been studied by mass spectrometry, using the kinetic method. With minor exceptions, the same relative order of BDE s is found for the three metals and the series of substituted arenes: electron‐donating substituents, like alkyl or amino groups, increase the arene−metal BDE whereas electron‐withdrawing substituents, e.g. halogens, lower the BDE compared to the unsubstituted benzene complexes. Interestingly, inverse linear correlations of the arene−M + BDE s and the arenes′ ionization energies (IEs) exist for particular classes of substituents. The present results may serve as a guide to predict BDE s of similar organometallic complexes based on the IEs of substituted arenes and vice versa.