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We should like to emphasize that the product distribution observed in these experiments does not unambiguously rule out that tA and cA react to different products: With our reactants cycloaddition is accompanied by geometric isomerization of the substrate to a large degree. so under conditions of preparative photolysis the system moves far towards the photostationary equilibrium between tA and cA regardless of whether the starting anethole is cA or tA. However, the same product distribution is also found in the CIDNP experiments described below, which are performed at very low conversion of the substrate.
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5344234876
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For photoinduced electron transfer sensitization in a similar reaction system see ref 13
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For photoinduced electron transfer sensitization in a similar reaction system see ref 13.
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50
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3tA or tA from the cation or the anion. This argument can be extended to isomerization via bond rotation in a triplet biradical followed by biradical cleavage
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3BR and all their subsequent products. In evaluations of relative polarizations stemming from the anethole radical cation only, this reaction is thus unimportant. The same argument can be used to explain why omission of escaping radical ions does not influence relative polarizations as long as no relaxation losses occur.
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