Rate constants and Arrhenius functions for hydrogen atom transfer from tert-butyl thiol to primary alkyl radicals

1989 ◽  
Vol 54 (19) ◽  
pp. 4603-4606 ◽  
Author(s):  
Martin Newcomb ◽  
Anne G. Glenn ◽  
M. Beata Manek
Keyword(s):  
Hydrogen Atom ◽  
Rate Constants ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Alkyl Radicals ◽  
Tert Butyl

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.

Arrhenius Parameters for Reaction of tert-Butylperoxy Radicals with some Hindered Phenols and Aromatic Amines

1973 ◽  
Vol 51 (22) ◽  
pp. 3738-3745 ◽  
Author(s):  
James Anthony Howard ◽  
Edward Furimsky
Keyword(s):  
Hydrogen Atom ◽  
Rate Constants ◽  
Aromatic Amines ◽  
Activation Parameters ◽  
Peroxy Radical ◽  
Hydrogen Atom Transfer ◽  
Tert Butyl ◽  
Radical Decay ◽  
Order Of Magnitude ◽  
Hindered Phenols

The reaction of tert-butylperoxy radicals with some 2,6-di-tert-butyl-4-substituted phenols, α-naphthol, α-naphthylamine, and N-phenyl-α-naphthylamine has been studied by following the change in radical concentration with time using an e.p.r. spectrometer. Rates of radical decay were first-order in both reactants and were not influenced by the presence of tert-butyl hydroperoxideAbsolute values of the second-order rate constants were measured from −35 to −100° and the preexponential factors and activation energies fell in the range 104–105 M−1 s−1 and 0.5–1.0 kcal mol−1. Rate constants for deuterated phenols (OD) and aromatic amines (ND) were an order of magnitude lower than for the corresponding light compoundsThere was no evidence for quantum mechanical tunneling in these hydrogen atom transfer reactions and it would appear that the activation parameters are low because reaction initially involves the formation of a hydrogen bonded peroxy radical – phenol (or aromatic amine) complex, followed by the transfer of a hydrogen atom within the complex

scholarly journals Titanium and Cobalt Bimetallic Radical Redox Relay for the Isomerization of N-Bz Aziridines to Allylic Amides

Synthesis ◽  
2021 ◽  
Author(s):  
Song Lin ◽  
Devin P. Wood ◽  
Weiyang Guan
Keyword(s):  
Hydrogen Atom ◽  
Hydrogen Atom Transfer ◽  
Alternative Strategy ◽  
Atom Transfer ◽  
Allylic Amination ◽  
Alkyl Radicals ◽  
Mild Conditions

AbstractHerein a bimetallic radical redox-relay strategy is employed to generate alkyl radicals under mild conditions with titanium(III) catalysis and terminated via hydrogen atom transfer with cobalt(II) catalysis to enact base-free isomerizations of N-Bz aziridines to N-Bz allylic amides. This reaction provides an alternative strategy for the synthesis of allylic amides from alkenes via a three-step sequence to accomplish a formal transpositional allylic amination.

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