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- W2007213410 abstract "Chemically induced dynamic nuclear spin polarizations (CIDNP) in the Paterno−Büchi cycloadducts of benzoquinone with norbornadiene or quadricyclane stem from a triplet biradical 3III with a norbornenyl substructure. Intersystem crossing of 3III and combination of the radical termini afford an oxolane I. By a cyclopropylmethyl−homoallyl rearrangement, 3III is converted into a Paterno−Büchi biradical 3IV, which after intersystem crossing yields an oxetane II. The ratio of nuclear spin polarizations in I and II strongly depends on temperature through the competition of nuclear spin relaxation in 3III with the biradical rearrangement. Using a kinetic treatment, a closed-form expression for the polarization ratio was derived. The activation energy of the cyclopropylmethyl−homoallyl rearrangement (17 ± 2 kJ/mol) was obtained from an evaluation of the CIDNP signals." @default.
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- W2007213410 date "2002-08-14" @default.
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- W2007213410 title "Activation Energy of a Biradical Rearrangement Measured by Photo-CIDNP" @default.
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- W2007213410 doi "https://doi.org/10.1021/jp020478k" @default.
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