Journal ArticleDOI
Rate Constants for the Addition of 2-Hydroxy-2-propyl Radicals to Alkenes in Solution studied by laser flash photolysis
TLDR
In this article, the absolute rate constants for the addition of the highly nucleophilic 2-hydroxy-2-propyl radical to eight fast-reacting 1-and 1,1-disubstituted alkenes in MeOH at room temperature have been determined by laser flash photolysis.Abstract:
Absolute rate constants for the addition of the highly nucleophilic 2-hydroxy-2-propyl radical to eight fast-reacting 1- and 1,1-disubstituted alkenes in MeOH at room temperature have been determined by laser flash photolysis. Also the absorption spectra of the 2-hydroxy-2-propyl and the benzylic and alkyl-type adduct radicals are presented. The rate constants were obtained using various methods for the analysis of the kinetic traces and support earlier findings.read more
Citations
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Journal ArticleDOI
Factors Controlling the Addition of Carbon‐Centered Radicals to Alkenes—An Experimental and Theoretical Perspective
Hanns Fischer,Leo Radom +1 more
TL;DR: The analysis leads to a partial revision of the previous qualitative rules, and it more clearly exhibits the interplay of the reaction enthalpy effects, polar charge-transfer contributions, and steric substituent effects on the reaction energy barrier.
Journal ArticleDOI
Cyclizations of Alkynes: Revisiting Baldwin’s Rules for Ring Closure
Kerry Gilmore,Igor V. Alabugin +1 more
Journal ArticleDOI
Entropy control of the cross-reaction between carbon-centered and nitroxide radicals.
TL;DR: Absolute rate constants for the cross-coupling reaction of several carbon-centered radicals with various nitroxides and their temperature dependence have been determined in liquids by kinetic absorption spectroscopy.
Journal ArticleDOI
Photochemistry and Photophysics of α-Hydroxy Ketones
TL;DR: In this paper, the photochemistry and photophysics of a series of derivatives of 2-hydroxy-2-methyl-1-phenyl propanone, a model photoinitiator for free radical polymerization, were investigated.
Journal ArticleDOI
Probing the reactivity of photoinitiators for free radical polymerization: time-resolved infrared spectroscopic study of benzoyl radicals.
Christopher S. Colley,David C. Grills,Nicholas A. Besley,Steffen Jockusch,Pavel Matousek,Anthony W. Parker,Michael Towrie,Nicholas J. Turro,Peter Gill,Michael W. George +9 more
TL;DR: The results support a mechanism in which the alpha-cleavage occurs from the triplet excited state that has a lifetime less than or equal to the singlet excited state.
References
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Journal ArticleDOI
Absolute Kinetics of Aminium Radical Reactions with Olefins in Acetonitrile Solution1
TL;DR: In this article, the authors measured the aminium radicals' lifetimes as a function of the concentration of added olefin, and absolute values for the bimolecular rate constants for the addition reactions were obtained.
Journal ArticleDOI
Rate constants for the addition of the 2-cyano-2-propyl radical to alkenes in solution
Károly Héberger,Hanns Fischer +1 more
TL;DR: The absolute rate constants for the addition of 2-cyano-2-propyl radical to 26 alkenes CH2=CXY at 315 K were determined in solution by time-resolved electron-spin-resonance spectroscopy.
Journal ArticleDOI
Assignment of Excited Electronic States of the Benzyl Radical by the Method of Three-Step Photoselection
TL;DR: In this article, the assignments of three excited states of the benzyl radical and some of its methyl derivatives are obtained by a method which involves an extension of the usual photoselection technique.
Journal ArticleDOI
Rate-determining step for decay of triplet biradicals: intersystem crossing vs. chain dynamics
TL;DR: In this article, the authors studied the temperature and viscosity dependence of the lifetimes of triplet biradicals derived from 2-phenylcycloalkanones by means of nanosecond transient UV absorption.
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