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

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About: The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies Goto Sponge NotDistinct Permalink

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
rdfs:seeAlso	http://pubs.acs.org/doi/abs/10.1021/ja407588p
Description	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 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)
Title	The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies (en)
skos:prefLabel	The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies The Pivotal Role of Oxyallyl Diradicals in Photo-Favorskii Rearrangements: Transient Spectroscopic and Computational Studies (en)
skos:notation	RIV/00216224:14310/13:00066642!RIV14-MSM-14310___
http://linked.open...avai/predkladatel	Přírodovědecká fakulta
http://linked.open...avai/riv/aktivita	P S
http://linked.open...avai/riv/aktivity	P(ED0001/01/01), P(GA13-25775S), P(LM2011028), S
http://linked.open...iv/cisloPeriodika	40
http://linked.open...vai/riv/dodaniDat	2014
http://linked.open...aciTvurceVysledku	Klán, Petr Šolomek, Tomáš Heger, Dominik Ngoy, Bokolombe Pitchou
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Masarykova univerzita / Přírodovědecká fakulta
http://linked.open...dnocenehoVysledku	96315
http://linked.open...ai/riv/idVysledku	RIV/00216224:14310/13:00066642
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	Photochemistry; Biradicals; Rearrangement (en)
http://linked.open.../riv/klicoveSlovo	Biradicals Photochemistry Rearrangement
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[E572E8442762]
http://linked.open...i/riv/nazevZdroje	Journal of the American Chemical Society
http://linked.open...in/vavai/riv/obor	CC
http://linked.open...ichTvurcuVysledku	4 (xsd:int)
http://linked.open...cetTvurcuVysledku	5 (xsd:int)
http://linked.open...vavai/riv/projekt	RECETOX – National research infrastructure for toxic compounds in the environment CETOCOEN Vývoj viditelným světlem aktivovatelných skupin a fluorescenčních značek pro chemii a biologii
http://linked.open...UplatneniVysledku	2013
http://linked.open...v/svazekPeriodika	135
http://linked.open...iv/tvurceVysledku	Klán, Petr Heger, Dominik Šolomek, Tomáš Givens, Richard Ngoy, Bokolombe Pitchou
http://linked.open...ain/vavai/riv/wos	000326356400046
issn	0002-7863
number of pages	7 (xsd:int)
http://bibframe.org/vocab/doi	10.1021/ja407588p
http://localhost/t...ganizacniJednotka	14310

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