In:
Canadian Journal of Chemistry, Canadian Science Publishing, Vol. 69, No. 5 ( 1991-05-01), p. 798-810
Abstract:
The rates of methyl transfer between benzohydroxamates and sulfonates show large β nuc values (ca. 0.8) indicating much charge transfer to the C atom, similar to the results of N,N-dialkylaminofluorene anions. A small α effect shows that even in methyl substrates, with certain leaving groups, the effect is displayed. Investigation of the β 1g shows that from the leaving group side of the reaction it is a normal S N 2 reaction. Correlation of the reactivity with computed gas phase ionization potentials shows that desolvation of anions is probably not important. These results suggest an α-effect model that explains the larger size of the effect at carbonyl groups in terms of greater solvation of the charge transferred to the O atom. Key words: α effect, Brønsted plot, ionization potentials, cyclic voltammetry, β 1g , β nuc , AMl, [Formula: see text]
Type of Medium:
Online Resource
ISSN:
0008-4042
,
1480-3291
Language:
English
Publisher:
Canadian Science Publishing
Publication Date:
1991
detail.hit.zdb_id:
1482256-8
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