A Novel Approach for Measuring Absolute Rate Constants by Pulsed Electron Spin Resonance:  Addition of Phosphinoyl and 2-Hydroxy-2-propyl Radicals to Several Alkenes†,‡

2003 ◽  
Vol 107 (18) ◽  
pp. 3326-3334 ◽  
Author(s):  
Matthias Weber ◽  
Nicholas J. Turro
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Rate Constants ◽  
Absolute Rate ◽  
Novel Approach ◽  
Spin Resonance

The Self-Reaction of sec-Alkylperoxy Radicals: A Kinetic Electron Spin Resonance Study

1972 ◽  
Vol 50 (14) ◽  
pp. 2374-2377 ◽  
Author(s):  
J. A. Howard ◽  
J. E. Bennett
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Rate Constants ◽  
The Self ◽  
Electron Spin Resonance Study ◽  
Absolute Rate ◽  
Arrhenius Plots ◽  
Spin Resonance ◽  
Alkylperoxy Radicals ◽  
Spin Resonance Study

Absolute rate constants for the self-reaction of cyclopentylperoxy, cyclopentenylperoxy, and sec-butylperoxyradicals have been determined over a 125 °C temperature range. Arrhenius plots derived from these rate constants suggest that the mechanism for this reaction is more complex than the currently accepted Russell mechanism.

An Electron Spin Resonance Study of Some Reactions of Pentafluorosulfuranyl (SF5)

1975 ◽  
Vol 53 (16) ◽  
pp. 2361-2364 ◽  
Author(s):  
John Charles Tait ◽  
James Anthony Howard
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Rate Constants ◽  
Arrhenius Equation ◽  
Kinetic Studies ◽  
Electron Spin Resonance Study ◽  
Order Process ◽  
First Order ◽  
Spin Resonance ◽  
Spin Resonance Study

A kinetic electron spin resonance study of the self-reaction of SF5 and a spectroscopic and kinetic e.s.r. study of the reaction of SF5 with 1,1-di-t-butylethylene are reported. This radical undergoes self-reaction by a second-order process and the rate constants are given by the Arrhenius equation log 2k1(M−1 s−1) = (10.3 ± 0.5) − (1.7 ± 0.5)/θ where θ = 2.303RT kcal mol−1. It adds to 1,1-di-t-butylethylene to give (t-Bu)2CCH2SF5 which decomposes by a first-order process with rate constants that obey the expression log k2(s−1) = (13 ± 0.4) − (10 ± 0.2)/θ. Both these rate constants are pertinent to kinetic studies of the photoinduced addition of SF5C1 to olefins.

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