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Versuche zur Berechnung kinetischer Isotopeneffekte II: Ein Vierzentren‐Modell des Übergangszutandes für die säurekatalytische Wasser‐Addition an Olefine
Author(s) -
Willi A. V.
Publication year - 1964
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.19640470232
Subject(s) - chemistry , olefin fiber , stereochemistry , catalysis , organic chemistry
The method of the preceding paper is applied to the transition state of the acid catalyzed olefin hydration. From different sets of force constants, vibration frequencies and partition function ratios are computed for a cyclic four center modelcomposed of olefin + H + ·OH 2 or olefin +D + ·OD 2 . Tunneling corrections are calculated with the aid of B ELL 'S formula. A semiempirical value is used for Q D3O / Q H3O . It is shown that for the four center transition state the isotope effect k H / k D may be in the order of 1.1–1.6.