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.

Základní údaje

Originální název

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

Autoři

ŠOLOMEK, Tomáš (703 Slovensko, domácí), Dominik HEGER (203 Česká republika, domácí), Bokolombe Pitchou NGOY (180 Konžská demokratická republika, domácí), Richard GIVENS (840 Spojené státy) a Petr KLÁN (203 Česká republika, garant, domácí)

Vydání

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

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10401 Organic chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 11.444

Kód RIV

RIV/00216224:14310/13:00066642

Organizační jednotka

Přírodovědecká fakulta

DOI

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

UT WoS

000326356400046

Klíčová slova anglicky

Photochemistry; Biradicals; Rearrangement

Štítky

AKR, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 13. 3. 2014 11:27, Mgr. Lucie Bláhová, Ph.D.

Anotace

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.

Návaznosti

ED0001/01/01, projekt VaV

Název: CETOCOEN

GA13-25775S, projekt VaV

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

Investor: Grantová agentura ČR, Vývoj viditelným světlem aktivovatelných skupin a fluorescenčních značek pro chemii a biologii

LM2011028, projekt VaV

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

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, RECETOX Národní infrastruktura pro výzkum toxických látek v prostředí

Citovat

ŠOLOMEK, Tomáš, Dominik HEGER, Bokolombe Pitchou NGOY, Richard GIVENS a 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, roč. 135, č. 40, s. 15209-15215. ISSN 0002-7863. Dostupné z: 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 a 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, roč.~135, č.~40, s.~15209-15215. ISSN~0002-7863. Dostupné z: https://dx.doi.org/10.1021/ja407588p.

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