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Properties and reactivity in groups of the periodic system: Ion‐molecule reactions CH 3 X + CH 3 X +· (X = F through At)
Author(s) -
Zahradník Rudolf,
Šroubková Libuše
Publication year - 1997
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19970800710
Subject(s) - chemistry , dimer , quantum chemical , halide , molecule , reactivity (psychology) , ion , electron , crystallography , computational chemistry , inorganic chemistry , organic chemistry , physics , medicine , alternative medicine , pathology , quantum mechanics
The reactions indicated in the title have been studied in terms of direct processes and complex formation. Quantum‐chemical methods have been applied to the passage of an acid (H + , CH 3 + , X + ) from CH 3 X +· to CH 3 X, and the abstraction of a radical (H · CH 3 · , X · ) from CH 3 X by CH 3 X +· . It has been shown that a complex represented by a dimer of a methyl‐halide radical cation, (CH 3 X) 2 +· , with a two‐center three‐electron bond XX, has fairly high stability. These investigations were based on non‐empirical quantum‐chemical calculations, the results being systematically compared with experimental determinations. Some calculations included all electrons (X=F, Cl, Br), others were based on relativistic pseudopotentials (X=F through At). The two sets of calculations agree qualitatively with each other and with experimental observations.