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Nuclear‐Spin Polarization in Electron‐Transfer Reactions of Amines
Author(s) -
Roth Heinz D.
Publication year - 2006
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200690258
Subject(s) - chemistry , cidnp , photochemistry , electron transfer , radical , dabco , triplet state , deprotonation , electron acceptor , intersystem crossing , ion , radical ion , naphthalene , electron , amine gas treating , polarization (electrochemistry) , excited state , molecule , organic chemistry , catalysis , atomic physics , quantum mechanics , physics , singlet state
Chemically induced dynamic nuclear polarization (CIDNP) observed during electron transfer (ET) reactions of tertiary amines such as DABCO ( 1 ) or Et 3 N ( 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 ( 1 Naph*), the resulting pair 2 . + /Naph .− reacts mostly by reverse electron transfer (RET) from triplet pairs populating the naphthalene triplet state.