Deuterium isotope effects in norcamphor metabolism by cytochrome P-450cam: kinetic evidence for the two-electron reduction of a high-valent iron-oxo intermediate

Biochemistry ◽  
1988 ◽  
Vol 27 (5) ◽  
pp. 1610-1616 ◽  
Author(s):  
William M. Atkins ◽  
Stephen G. Sligar
Keyword(s):  
Isotope Effects ◽  
Deuterium Isotope Effects ◽  
Electron Reduction ◽  
High Valent

Kinetics and mechanism of the oxidation of alcohols by ruthenate and perruthenate ions

1990 ◽  
Vol 68 (10) ◽  
pp. 1774-1779 ◽  
Author(s):  
Donald G. Lee ◽  
Ligaya N. Congson
Keyword(s):  
Organic Chemistry ◽  
Free Radical ◽  
Transition Metal ◽  
Metal Ions ◽  
Mandelic Acid ◽  
Isotope Effects ◽  
Transition Metal Ions ◽  
Oxidation Of Alcohols ◽  
Deuterium Isotope Effects ◽  
High Valent

In addition to being important synthetic reagents, ruthenate and perruthenate are of interest because they are representative of a number of high valent transition metal ions that can be used as oxidants in organic chemistry. In their reactions with alcohols both ions exhibit several striking similarities — concave Hammett plots, primary deuterium isotope effects, small enthalpies of activation, and large negative entropies of activation. The most likely explanation of the concave upward Hammett plots is the involvement of free radical-like transition states that could be formed by the decomposition of organometallic intermediates. Keywords: oxidation, ruthenate, perruthenate, alcohols, mandelic acid.

Mechanism of hydration and isomerisation of 4-ethylidene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one. Kinetics, acid-base catalysis and solvent deuterium isotope effects

1979 ◽  
Vol 44 (1) ◽  
pp. 110-122 ◽  
Author(s):  
Jiří Velek ◽  
Bohumír Koutek ◽  
Milan Souček
Keyword(s):  
Aqueous Medium ◽  
Rate Equation ◽  
Kinetic Data ◽  
Isotope Effects ◽  
Base Catalysis ◽  
Quinone Methide ◽  
Reaction Products ◽  
Acid Base ◽  
Deuterium Isotope Effects ◽  
Hydroxybenzyl Alcohol

Competitive hydration and isomerisation of the quinone methide I at 25 °C in an aqueous medium in the region of pH 2.4-13.0 was studied spectrophotometrically. The only reaction products in the studied range of pH are 4-hydroxybenzyl alcohol (II) and 4-hydroxystyrene (III). The form of the overall rate equation corresponds to a general acid-base catalysis. The mechanism of both reactions for three markedly separated pH regions is discussed on the basis of kinetic data and solvent deuterium effect.

Hydrogen/Deuterium-Isotope Effects on NMR Chemical Shifts and Symmetry of Homoconjugated Hydrogen-Bonded Ions in Polar Solution

2000 ◽  
Vol 122 (51) ◽  
pp. 12878-12879 ◽  
Author(s):  
Parwin Schah-Mohammedi ◽  
Ilja G. Shenderovich ◽  
Carsten Detering ◽  
Hans-Heinrich Limbach ◽  
Peter M. Tolstoy ◽  
...  
Keyword(s):  
Chemical Shifts ◽  
Isotope Effects ◽  
Polar Solution ◽  
Nmr Chemical Shifts ◽  
Hydrogen Deuterium ◽  
Deuterium Isotope Effects ◽  
Hydrogen Bonded
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