Abstract

AbstractChemically induced dynamic nuclear polarization (CIDNP) observed during electron transfer (ET) reactions of tertiary amines such as DABCO (1) or Et3N (2) with a wide range of electron acceptors support the involvement of amine radical‐cations (e.g., 1.+ or 2.+) as key intermediates. Radical ions such as 2.+ may be deprotonated, generating neutral aminoalkyl radicals (e.g., 2.). When generated by reaction with an electron acceptor of energetically low triplet state such as naphthalene (1Naph*), the resulting pair 2.+/Naph.− reacts mostly by reverse electron transfer (RET) from triplet pairs populating the naphthalene triplet state.

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