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Mechanistic Aspects of the Gas‐Phase Reactions of Halobenzenes with Bare Lanthanide Cations: A Combined Experimental/Theoretical Investigation
Author(s) -
Zhou Shaodong,
Schlangen Maria,
Schwarz Helmut
Publication year - 2015
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.201405964
Subject(s) - lanthanide , chemistry , chlorobenzene , fluorobenzene , fourier transform ion cyclotron resonance , chlorine , density functional theory , dissociation (chemistry) , thermochemistry , ion , bond dissociation energy , ion cyclotron resonance , mass spectrometry , bond energy , fluorine , inorganic chemistry , computational chemistry , photochemistry , analytical chemistry (journal) , molecule , benzene , organic chemistry , catalysis , cyclotron , chromatography
The gas‐phase reactions of chlorobenzene with all atomic lanthanide cations Ln + (except Pm + ) have been investigated by using Fourier transform ion cyclotron resonance mass spectrometry in conjunction with density functional theory calculations. According to the latter, a direct chlorine transfer to the lanthanide cation, which has been observed previously for fluorine abstraction from fluorobenzene, is not operative for the C 6 H 5 Cl/Ln + couples; rather, chlorine transfer proceeds through an initial coordination of the lanthanide cation to the aromatic ring of the substrate. Both, the product distribution and the chlorine abstraction efficiencies are affected by the bond dissociation energy (BDE(Ln + Cl)) as well as the promotion energies of Ln + to attain a 4f n 5d 1 6s 1 configuration. In addition, mechanistic aspects of some CH and CC bond activations are presented. Where appropriate, comparison with the previously studied C 6 H 5 F/Ln + systems is made.