The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii
Rearrangements: Transient Spectroscopic and Computational
Studies

J 2013

The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies

ŠOLOMEK, Tomáš, Dominik HEGER, Bokolombe Pitchou NGOY, Richard GIVENS, Petr KLÁN et. al.

Basic information

Original name

The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies

Authors

ŠOLOMEK, Tomáš (703 Slovakia, belonging to the institution), Dominik HEGER (203 Czech Republic, belonging to the institution), Bokolombe Pitchou NGOY (180 Democratic Republic of the Congo, belonging to the institution), Richard GIVENS (840 United States of America) and Petr KLÁN (203 Czech Republic, guarantor, belonging to the institution)

Edition

Journal of the American Chemical Society, Washington, DC., USA, American Chemical Society, 2013, 0002-7863

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10401 Organic chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 11.444

RIV identification code

RIV/00216224:14310/13:00066642

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1021/ja407588p

UT WoS

000326356400046

Keywords in English

Photochemistry; Biradicals; Rearrangement

Abstract

V originále

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.

Links

ED0001/01/01, research and development project

Name: CETOCOEN

GA13-25775S, research and development project

Name: Vývoj viditelným světlem aktivovatelných skupin a fluorescenčních značek pro chemii a biologii

Investor: Czech Science Foundation

LM2011028, research and development project

Name: RECETOX ? Národní infrastruktura pro výzkum toxických látek v prostředí

Investor: Ministry of Education, Youth and Sports of the CR

Citovat

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.

@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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