PMID: 11925239Apr 2, 2002Paper

Spectral properties and absolute rate constants for beta-scission of ring-substituted cumyloxyl radicals. A laser flash photolysis study

The Journal of Organic Chemistry
Enrico BaciocchiSteen Steenken

Abstract

A laser flash photolysis study of the spectral properties and beta-scission reactions of a series of ring-substituted cumyloxyl radicals has been carried out. All cumyloxyl radicals display a broad absorption band in the visible region of the spectrum, which decays on the microsecond time scale, leading to a strong increase in absorption in the UV region of the spectrum, which is attributed to the corresponding acetophenone formed after beta-scission of the cumyloxyl radicals. The position of the visible absorption band is red-shifted by the presence of electron-donating ring substituents, while a blue-shift is observed in the presence of electron-withdrawing ring substituents, suggesting that + R ring substituents promote charge separation in the excited cumyloxyl radical through stabilization of the partial positive charge on the aromatic ring of an incipient radical zwitterion. Along this line, an excellent Hammett-type correlation between the experimentally measured energies at the visible absorption maxima of the cumyloxyl radicals and sigma(+) substituent constants is obtained. A red-shift is also observed on going from MeCN to MeCN/H(2)O for all cumyloxyl radicals, pointing toward a specific effect of water. The ring sub...Continue Reading

References

Oct 25, 2001·The Journal of Organic Chemistry·Sarah WilseyK. N. Houk

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Citations

Feb 5, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Tetsuro TanoShinobu Itoh
Aug 3, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Tetsuro TanoShinobu Itoh
Jul 9, 2009·Organic Letters·Lu-An Chen, Kuangsen Sung
Oct 11, 2017·The Journal of Physical Chemistry. a·Marwa K Abdel LatifJames M Tanko
Nov 25, 2017·The Journal of Physical Chemistry. a·Kazumasa OkamotoTakahiro Kozawa
Jan 23, 2019·The Journal of Physical Chemistry. a·Meisam Farzalipour TabrizErsin Yurtsever
Aug 19, 2007·The Journal of Physical Chemistry. a·Kurt A Kistler, Spiridoula Matsika
Nov 26, 2002·The Journal of Organic Chemistry·Martin NewcombJohn H Horner
Jun 17, 2004·Journal of the American Chemical Society·Meghan FinnJames M Tanko
May 21, 2005·The Journal of Organic Chemistry·Michihiro HaraTetsuro Majima
Dec 6, 2005·The Journal of Organic Chemistry·Massimo Bietti, Michela Salamone
Oct 7, 2021·Chemical Reviews·Liang ChangZhiwei Zuo

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