116597-11-6Relevant articles and documents
Proton-Electron Transfer: Kinetics and Mechanism in the Ketone-Ketyl Redox System
Naguib, Yousry M. A.,Steel, Colin,Cohen, Saul G.
, p. 6574 - 6579 (1988)
Rate constants for the two ketyl-ketone redox systems AH. + K -> A + KH. (7) and K*H. + K -> K* + KH. (14), where AH., K*H., KH., K, and A are dimethylketyl (Me2C.OH), 4-tert-butyldiphenylketyl, diphenylketyl (Ph2C.OH), benzophenone, and acetone, are k7 = (3.5 +/- 1.5) * 104 M-1 s-1 and k14 = (1.5 +/- 0.2) * 104 M-1 s-1* at 298 K.The value for k7 is significantly lower than previous literature reports for this number.However, the current values for both k7 and k14 are consistent with considerable chemical evidence from other sources.It is shown that these reactions, although formally hydrogen transfers, cannot occur by a "normal" H atom transfer.They also do not occur by sequential transfer of a proton followed by an electron, or vice versa.Instead it is proposed that the carbonyl acts as a dual-site receptor for proton and electron transfer from the dual-site donor, the reducing ketyl radical.