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- W2034551427 endingPage "1965" @default.
- W2034551427 startingPage "1952" @default.
- W2034551427 abstract "On ultraviolet irradiation of the cyclopent-2-enyl methyl ketones 1a–c at −54° ⩽ t ⩽ 139°, photo-CIDNP. effects of the starting ketones, the 1,3-acetyl shifted isomers (2), and radical disproportionation and combination products (4–7) were observed. These effects show a unique dependence of the polarization phase on temperature which is a novel feature in photo-CIDNP. studies. The results of the investigation, which also included experiments using triplet quenchers, triplet sensitizers and radical scavengers, are rationalized in terms of Schemes 2 and 3. α-Cleavage is a major excited-state reaction of 1a–c on direct irradiation. Temperature-activated α-cleavage (k(t)) to the radical pair R · · R′1 and intersystem crossing (kisc) to the T2 state are among the competing S1 deactivation processes. The T2 state in turn cleaves (k) to R · · R′3 A ‘low-temperature range’ with kisc ≫ k(t) and a ‘high-temperature range’ with k(t) ≫ kisc exhibiting preferential reactivity from the T2 and S1 states, respectively, can be defined for all three β,γ-unsaturated ketones 1a–c." @default.
- W2034551427 created "2016-06-24" @default.
- W2034551427 creator A5026666871 @default.
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- W2034551427 date "1979-09-19" @default.
- W2034551427 modified "2023-10-03" @default.
- W2034551427 title "Photo-CIDNP. Investigation of ?,?-Unsaturated Ketones: Evidence for Temperature-dependent S1vs. T2 Reactivities of Cyclopent-2-enyl Methyl Ketones" @default.
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- W2034551427 doi "https://doi.org/10.1002/hlca.19790620624" @default.
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