42439-31-6Relevant articles and documents
Time-Resolved Resonance Raman Observation of Tetrafluoro-p-benzosemiquinone Anion Radical
Tripathi, G. N. R.,Schuler, Robert H.
, p. 3101 - 3105 (1983)
Time-resolved resonance Raman spectroscopy has been used to examine tetrafluoro-p-benzosemiquinone radical anion produced in the pulse radiolytic oxidation of tetraflourohydroquinone in aqueous solution.This radical is much more reactive than p-benzosemiquinone and is observed to decay on the millisecond time scale in both Raman and pulse radiolytic experiments.For the Raman experiments excitation was on the red edge of the moderately strong absorption band of this radical at 430 nm.Two resonance-enhanced Raman bands are exhibited at 1556 and 1677 cm-1 and are assigned to the in-phase CO and symmetrical CC stretch vibrations.These frequencies are considerably higher than the corresponding values of 1435 and 1620 cm-1 observed in this radical's protonated counterpart.The relatively large increase in the CO stretch frequency, in particular, indicates that fluorination induces a substantial increase in the quinoid character of this radical.
Electron-transfer studies of a peroxide dianion
Ullman, Andrew M.,Sun, Xianru,Graham, Daniel J.,Lopez, Nazario,Nava, Matthew,De Las Cuevas, Rebecca,Mueller, Peter,Rybak-Akimova, Elena V.,Cummins, Christopher C.,Nocera, Daniel G.
supporting information, p. 5384 - 5391 (2014/06/09)
A peroxide dianion (O22-) can be isolated within the cavity of hexacarboxamide cryptand, [(O2)∪mBDCA-5t-H 6]2-, stabilized by hydrogen bonding but otherwise free of proton or metal-ion association. This feature has allowed the electron-transfer (ET) kinetics of isolated peroxide to be examined chemically and electrochemically. The ET of [(O2)∪mBDCA-5t-H6] 2- with a series of seven quinones, with reduction potentials spanning 1 V, has been examined by stopped-flow spectroscopy. The kinetics of the homogeneous ET reaction has been correlated to heterogeneous ET kinetics as measured electrochemically to provide a unified description of ET between the Butler-Volmer and Marcus models. The chemical and electrochemical oxidation kinetics together indicate that the oxidative ET of O22- occurs by an outer-sphere mechanism that exhibits significant nonadiabatic character, suggesting that the highest occupied molecular orbital of O 22- within the cryptand is sterically shielded from the oxidizing species. An understanding of the ET chemistry of a free peroxide dianion will be useful in studies of metal-air batteries and the use of [(O 2)∪mBDCA-5t-H6]2- as a chemical reagent.
Oxidation mechanism of NAD dimer model compounds
Patz, Matthias,Kuwahara, Yoshihiro,Suenobu, Tomoyoshi,Fukuzumi, Shunichi
, p. 567 - 568 (2007/10/03)
The oxidation of a dimeric N-benzyldihydronicotinamide with various oxidants such as quinones, triphenyl carbenium ions and a triplet exited tris(bipyridine) ruthenium(II) complex occurs via initial outer-sphere electron transfer followed by fast C-C bond cleavage and second electron transfer. The kinetic studies allow the determination of the oxidation potential of this compound.