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Fast Interconversion of C 4 H 7 + Cations in the Gas Phase and in a Gaseous Microsolvated Environment
Author(s) -
Cacace Fulvio,
Chiavarino Barbara,
Crestoni M. Elisa
Publication year - 2000
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 - 10.1002/1521-3765(20000602)6:11<2024::aid-chem2024>3.0.co;2-1
Subject(s) - chemistry , gas phase , intermolecular force , solvent , radiolysis , nucleophile , ion , phase (matter) , molecule , trapping , inorganic chemistry , analytical chemistry (journal) , radical , organic chemistry , catalysis , ecology , biology
The equilibration of cyclobutyl 1 and 1′ and the cyclopropylmethyl cation ( 2 ) has been studied in the gas phase by utilizing FT‐ICR mass spectrometry and high‐pressure radiolytic techniques. A suitable gaseous nucleophile, C 6 X 6 (X=H,D), was used to sample the equilibration of C 4 H 7 + ions, produced from both cyclobutanol and cyclopropylmethanol. These are either dispersed in the bulk gas or confined within a C 4 H 7 + /C 6 X 6 complex that contains a molecule of solvent (H 2 O). The analysis of the products shows that, irrespective of their source and of the intermolecular or intracomplex nature of the process, the C 4 H 7 + ions undergo equilibration before they are trapped. The equilibrium ( 1 + 1′ )/ 2 ratio is very close to unity at 300 K, and the results from the intracomplex trapping experiment show that equilibration occurs within a time interval ≤10 −10 s.