"http://pubs.acs.org/doi/abs/10.1021/ja407588p" . "Ngoy, Bokolombe Pitchou" . . "[E572E8442762]" . "US - Spojen\u00E9 st\u00E1ty americk\u00E9" . . "The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies" . "14310" . "The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies"@en . . "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." . "The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies" . . "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."@en . "0002-7863" . . "P(ED0001/01/01), P(GA13-25775S), P(LM2011028), S" . . . "40" . "Photochemistry; Biradicals; Rearrangement"@en . "RIV/00216224:14310/13:00066642!RIV14-MSM-14310___" . "Journal of the American Chemical Society" . . "4"^^ . "RIV/00216224:14310/13:00066642" . . . "000326356400046" . "Kl\u00E1n, Petr" . . "The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies"@en . . . . . . . "5"^^ . "135" . "96315" . "\u0160olomek, Tom\u00E1\u0161" . "Heger, Dominik" . "7"^^ . . . . . . "Givens, Richard" . "10.1021/ja407588p" .