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Primary and Secondary Isotope Effects on Proton Transfers to Diazocarbonyl Compounds
Author(s) -
McGarrity John F.
Publication year - 1980
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.19800630703
Subject(s) - chemistry , kinetic isotope effect , solvent , primary (astronomy) , proton , reactivity (psychology) , solvation , isotope , hydrolysis , substrate (aquarium) , computational chemistry , medicinal chemistry , organic chemistry , stereochemistry , radiochemistry , deuterium , quantum mechanics , medicine , physics , alternative medicine , oceanography , astronomy , pathology , geology
The primary solvent isotope effects on the AS E ‐2 type hydrolyses of α‐diazocarbonyl compounds p ‐XC 6 H 4 CN 2 CH 3 (X = NO 2 , H, OCH 3 and C 6 H 5 CON(CH 3 ) 2 ) are found to be identical despite large differences in their overall hydrolysis rates. The secondary solvent isotope effects diminish considerably with diminishing substrate reactivity, and for two substrates they are smaller than those normally anticipated for a simple proton transfer from the lyonium species. An analysis is presented of these and other abnormal secondary isotope effects found elsewhere, involving consideration of the solvation of the reaction complex.