No Contribution of an Inductive Effect to Secondary Deuterium Isotope Effects on Acidity
✍ Scribed by Prof. Charles L. Perrin; Agnes Flach
- Publisher
- John Wiley and Sons
- Year
- 2011
- Tongue
- English
- Weight
- 274 KB
- Volume
- 50
- Category
- Article
- ISSN
- 0044-8249
No coin nor oath required. For personal study only.
✦ Synopsis
Isotope effects are observed when a reaction rate or equilibrium constant changes as a result of isotopic substitution. [1] They continue to be used as valuable tools to provide insight into molecular structure and reactivity. [2] Secondary isotope effects are those in which the bond to the isotope remains intact. Their origin continues to be an area of investigation. [3] Herein we address the origin of secondary deuterium isotope effects on acidity.
Deuterium isotope effects on acidities are expressed as K a H /K a D or as DpK = Àlog 10 (K a H
📜 SIMILAR VOLUMES
## Abstract Reaction rates for the protodesilylation of trimethylphenylsilane and of [2,4,6‐^2^H~3~]‐trimethylphenylsilane by HCIO~4~, were measured in aqueous methanol (2:5, __v/v__) and the secondary deuterium isotope effect for the reaction was found to be __k__~H~/__k__~D3~ = 0.79. The magnitud
## Abstract Deuterium isotope effects on ^13^C chemical shift of tetrabutylammonium salts of Schiff bases, derivatives of amino acids (glycine, L‐alanine, L‐phenylalanine, L‐valine, L‐leucine, L‐isoleucine and L‐methionine) and various ortho‐hydroxyaldehydes in CDCl~3~ have been measured. The resul
## Synopsis llilferences in refractive index between deuterated and normal solvents have been determined using a conventional gel permeation chromatograph equipped with a differential refractometer detector. Three molecular systems have been studied, namely, walerdeuterium oxide, acetone-acetone (
Deuterium substitution at remote sites gives rise to inverse secondary kinetic isotope effects on the a-cleavage of a number of tertiary amines in the ion source, but to normal isotope effects on reactions occurring in the field-free regions. The change from normal to inverse secondary isotope effec