| ŠOLOMEK, Tomáš, Dominik HEGER, Bokolombe Pitchou NGOY, Richard GIVENS and Petr KLÁN. The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies. Journal of the American Chemical Society. Washington, DC., USA: American Chemical Society, 2013, vol. 135, No 40, p. 15209-15215. ISSN 0002-7863. Available from: https://dx.doi.org/10.1021/ja407588p. |
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@article{1138374,
author = {Šolomek, Tomáš and Heger, Dominik and Ngoy, Bokolombe Pitchou and Givens, Richard and Klán, Petr},
article_location = {Washington, DC., USA},
article_number = {40},
doi = {http://dx.doi.org/10.1021/ja407588p},
keywords = {Photochemistry; Biradicals; Rearrangement},
language = {eng},
issn = {0002-7863},
journal = {Journal of the American Chemical Society},
title = {The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies},
url = {http://pubs.acs.org/doi/abs/10.1021/ja407588p},
volume = {135},
year = {2013}
}
TY - JOUR
ID - 1138374
AU - Šolomek, Tomáš - Heger, Dominik - Ngoy, Bokolombe Pitchou - Givens, Richard - Klán, Petr
PY - 2013
TI - The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies
JF - Journal of the American Chemical Society
VL - 135
IS - 40
SP - 15209-15215
EP - 15209-15215
PB - American Chemical Society
SN - 00027863
KW - Photochemistry
KW - Biradicals
KW - Rearrangement
UR - http://pubs.acs.org/doi/abs/10.1021/ja407588p
L2 - http://pubs.acs.org/doi/abs/10.1021/ja407588p
N2 - The photochemistry of the hydroxybenzocycloalkanonyl derivatives 6b-e provides the triplet oxyallyl diradicals (3)9 that decay via intersystem crossing to their more stable singlet isomers (1)9. Vibrationally resolved transient spectra of 39 were recorded by pump-probe spectroscopy and laser flash photolysis. It was found that the ring strain dependent rate of intersystem crossing is the rate-limiting step in the formation of photo-Favorskii or solvolysis reaction products in water. The reactivities of open-shell singlet oxyallyls (1)9a-e determine the product ratios due to their relative abilities to form the corresponding cyclopropanones 10. The smallest five-membered derivative, (1)9b, represents the first example of an oxyallyl diradicaloid that cannot form cyclopropanone 10b or the isomeric allene oxide 13b; instead, it is eventually trapped by water to form the sole solvolysis product 12b. Our observations provide a comprehensive overview of the role of oxyallyl diradicals in reaction mechanisms and offer a new strategy to stabilize open-shell singlet diradicals.
ER -
ŠOLOMEK, Tomáš, Dominik HEGER, Bokolombe Pitchou NGOY, Richard GIVENS and Petr KLÁN. The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies. \textit{Journal of the American Chemical Society}. Washington, DC., USA: American Chemical Society, 2013, vol.~135, No~40, p.~15209-15215. ISSN~0002-7863. Available from: https://dx.doi.org/10.1021/ja407588p.
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