Determination of absolute rate constants for the reversible hydrogen-atom transfer between thiyl radicals and alcohols or ethers

1995 ◽  
Vol 91 (13) ◽  
pp. 1923-1930 ◽  
Author(s):  
Christian Schöneich ◽  
Klaus-Dieter Asmus ◽  
Marija Bonifačić
Keyword(s):  
Hydrogen Atom ◽  
Rate Constants ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Absolute Rate ◽  
Thiyl Radicals

scholarly journals Absolute rate constants for hydrocarbon autoxidation. 26. Rate constants for reaction of the tert-butylperoxy radical with 1-bromo-2-methylbutane and 1-bromo-3-methylbutane and some related substituted butanes

1979 ◽  
Vol 57 (18) ◽  
pp. 2484-2490 ◽  
Author(s):  
J. A. Howard ◽  
J. H. B. Chenier
Keyword(s):  
Hydrogen Atom ◽  
Transition State ◽  
Kinetic Parameters ◽  
Rate Constants ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Absolute Rate ◽  
Arrhenius Parameters

Rate constants and Arrhenius parameters for reaction of the tert-butylperoxy radical with 1-bromo-2-methylbutane and 1-bromo-3-methylbutane in solution from 30–80 °C have been estimated. The magnitude of these kinetic parameters are consistent with activation of the tertiary hydrogen vicinal to the bromine substituent and the involvement of a "bridged" transition state in the hydrogen atom transfer reaction.Chloro, trimethylsilyl, and trimethylstannyl substituents also activate a vicinal tertiary hydrogen and activation increases in the order trimethylsilyl ∼ trimethylstannyl < chloro < bromo.

Experimental Validation of Hydrogen Atom Transfer Gibbs Free Energy as a Predictor of Nitroaromatic Reduction Rate Constants

2019 ◽  
Vol 53 (10) ◽  
pp. 5816-5827 ◽  
Author(s):  
Jimmy Murillo-Gelvez ◽  
Kevin P. Hickey ◽  
Dominic M. Di Toro ◽  
Herbert E. Allen ◽  
Richard F. Carbonaro ◽  
...  
Keyword(s):  
Free Energy ◽  
Hydrogen Atom ◽  
Gibbs Free Energy ◽  
Rate Constants ◽  
Experimental Validation ◽  
Reduction Rate ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer

Hydrogen Atom Transfer Rates from Tp-Containing Metal Hydrides to Trityl Radicals

2020 ◽  
Author(s):  
Hunter B. Vibbert ◽  
Hagen Neugebauer ◽  
Jack R Norton ◽  
Andreas Hansen ◽  
Markus Bursch ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Rate Constants ◽  
Transfer Rate ◽  
Metal Hydrides ◽  
Hydrogen Atom Transfer ◽  
Transfer Reactions ◽  
Atom Transfer ◽  
Transfer Rates ◽  
Borate Complexes ◽  
And Tungsten

The H• transfer rate constants for a series of group 6 molybdenum and tungsten pyrazolyl borate complexes are described. The rate constants for these complexes were found to span a range over 1 magnitude. Analysis of the H• transfer rate constants suggests that a combination of steric, electronic, and enthalpic factors are important in these reactions. Further analysis of the components suggests that the generated 17 e– radicals of these complexes are less electrophilic than the more commonly used CpCr(CO)3H complexes. General implications for H• transfer reactions are discussed.

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