Primary and secondary β-deuterium kinetic isotope effects in the 1,3-prototropic rearrangement of 1-methylindene using tertiary amines as catalysts in the solvents toluene and dimethyl sulphoxide

1985 ◽  
pp. 221-226 ◽  
Author(s):  
Olle Matsson
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Dimethyl Sulphoxide ◽  
Tertiary Amines ◽  
Kinetic Isotope ◽  
Prototropic Rearrangement

scholarly journals Formation of Enamines via Catalytic Dehydrogenation by Pincer-Iridium Complexes

2019 ◽  
Author(s):  
Xiawei Zhang ◽  
Santanu Malakar ◽  
Karsten Krogh-Jespersen ◽  
Faraj Hasanayn ◽  
Alan Goldman
Keyword(s):  
Isotope Effects ◽  
Oxidative Addition ◽  
Kinetic Isotope Effects ◽  
Catalytic Dehydrogenation ◽  
Iridium Complexes ◽  
Tertiary Amines ◽  
Iridium Catalysts ◽  
Kinetic Isotope ◽  
Dehydrogenation Mechanism

Efficient pincer-ligated iridium catalysts are reported for the dehydrogenation of simple tertiary amines to give enamines, and for the dehydrogenation of β-functionalized amines to give the corresponding 1,2-difunctionalized olefins. Experimentally determined kinetic isotope effects in conjunction with DFT-based analysis support a dehydrogenation mechanism involving initial pre-equilibrium oxidative addition of the amine α C-H bond followed by rate-determining elimination of the β-C-H bond.<br>

scholarly journals Formation of Enamines via Catalytic Dehydrogenation by Pincer-Iridium Complexes

2019 ◽  
Author(s):  
Xiawei Zhang ◽  
Santanu Malakar ◽  
Karsten Krogh-Jespersen ◽  
Faraj Hasanayn ◽  
Alan Goldman
Keyword(s):  
Isotope Effects ◽  
Oxidative Addition ◽  
Kinetic Isotope Effects ◽  
Catalytic Dehydrogenation ◽  
Iridium Complexes ◽  
Tertiary Amines ◽  
Iridium Catalysts ◽  
Kinetic Isotope ◽  
Dehydrogenation Mechanism

Efficient pincer-ligated iridium catalysts are reported for the dehydrogenation of simple tertiary amines to give enamines, and for the dehydrogenation of β-functionalized amines to give the corresponding 1,2-difunctionalized olefins. Experimentally determined kinetic isotope effects in conjunction with DFT-based analysis support a dehydrogenation mechanism involving initial pre-equilibrium oxidative addition of the amine α C-H bond followed by rate-determining elimination of the β-C-H bond.<br>

SECONDARY KINETIC ISOTOPE EFFECTS IN BIMOLECULAR NUCLEOPHILIC SUBSTITUTIONS: II. α-DEUTERIUM EFFECTS IN MENSCHUTKIN REACTIONS OF METHYL IODIDE

1965 ◽  
Vol 43 (1) ◽  
pp. 40-46 ◽  
Author(s):  
K. T. Leffek ◽  
J. W. MacLean
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Systematic Change ◽  
Tertiary Amines ◽  
Nucleophilic Substitutions ◽  
Methyl Group ◽  
Kinetic Isotope ◽  
Deuterium Substitution ◽  
Different Temperatures ◽  
Rate Ratios

Secondary deuterium isotope effects have been measured for the reactions between methyl and methyl-d3 iodides and a series of tertiary amines in benzene solvent. Deuterium substitution increased the rate of each reaction but the rate ratios (kH/kD) show no systematic change with variation in the structure of the amine. The isotope effect for the reaction with 2-picoline was measured at different temperatures over a range of 40 deg and shows no change. These isotope effects may be rationalized as internal rotational effects of the methyl group or as solvation effects.

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