Abstract: | Chemically 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. |