TY - JOUR
T1 - Outer-sphere electron-transfer oxidation of 10,10′-dimethyl-9,9′,10,10′-tetrahydro-9,9′-biacridine
AU - Fukuzumi, Shunichi
AU - Tokuda, Yoshihiro
PY - 1992
Y1 - 1992
N2 - 10,10′-Dimethyl-9,9′,10,10′-tetrahydro-9,9′- biacridine [(ACrH)2] acts as a unique two-electron donor in the electron-transfer oxidation with various organic oxidants. The rate-determining step is electron transfer from (AcrH)2 to oxidants, followed by facile cleavage of the C(9)-C bond of (AcrH)2.+ to yield the acridinyl radical (AcrH.) and 10-methylacridinium ion (AcrH+). The second electron transfer from AcrH. to oxidants is much faster than the initial electron transfer from (AcrH)2 to oxidants. On the other hand, the corresponding monomer, 10-methyl-9,10-dihydroacridine (AcrH2), acts as a normal hydride (two electrons and proton) donor in the reactions with oxidants. Rates of electron-transfer reactions from (AcrH)2 to various inorganic and organic one-electron oxidants depend solely on the one-electron-reduction potentials of the oxidants irrespective of the size of the oxidants, indicating that (ACrH)2 acts as a novel two-electron outer-sphere electron-transfer reagent. The one-electron-oxidation potential of (AcrH)2 (vs SCE) has been evaluated as 0.62 V, which is less positive than that of the corresponding monomer (0.80 V).
AB - 10,10′-Dimethyl-9,9′,10,10′-tetrahydro-9,9′- biacridine [(ACrH)2] acts as a unique two-electron donor in the electron-transfer oxidation with various organic oxidants. The rate-determining step is electron transfer from (AcrH)2 to oxidants, followed by facile cleavage of the C(9)-C bond of (AcrH)2.+ to yield the acridinyl radical (AcrH.) and 10-methylacridinium ion (AcrH+). The second electron transfer from AcrH. to oxidants is much faster than the initial electron transfer from (AcrH)2 to oxidants. On the other hand, the corresponding monomer, 10-methyl-9,10-dihydroacridine (AcrH2), acts as a normal hydride (two electrons and proton) donor in the reactions with oxidants. Rates of electron-transfer reactions from (AcrH)2 to various inorganic and organic one-electron oxidants depend solely on the one-electron-reduction potentials of the oxidants irrespective of the size of the oxidants, indicating that (ACrH)2 acts as a novel two-electron outer-sphere electron-transfer reagent. The one-electron-oxidation potential of (AcrH)2 (vs SCE) has been evaluated as 0.62 V, which is less positive than that of the corresponding monomer (0.80 V).
UR - http://www.scopus.com/inward/record.url?scp=0000313758&partnerID=8YFLogxK
U2 - 10.1021/j100200a037
DO - 10.1021/j100200a037
M3 - Article
AN - SCOPUS:0000313758
SN - 0022-3654
VL - 96
SP - 8409
EP - 8413
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
IS - 21
ER -