70594-57-9Relevant academic research and scientific papers
Structure and reactivity of perfluorinated branched α-ketoradicals
Tumanskii,Shaposhnikova,Avetisyan,Sterlin
, p. 47 - 50 (1999)
Fluoroaliphatic hydroxyketoradicals prepared by photochemical reduction of the corresponding α-diketones and (i-C3F7)2CC(O)CF3 react with hydrogen abstraction (according to ESR data). The hydroxyketor
Chemical dynamics of the reaction between chlorine atoms and deuterated cyclohexane
Park, Jeunghee,Lee, Yongsik,Hershberger, John F.,Hosseolopp, Jeanne M.,Flynn, George W.
, p. 58 - 63 (1992)
The dynamics of the reaction Cl + cyclohexane-d12 (c-C6D12) → DCl + C6D11 have been investigated by using time-resolved diode laser absorption spectroscopy to probe the reaction product DCl. The chlorine atoms have been generated by the UV photolysis of S2C12 and NOCl. Nascent DCl produced in the reaction is rotationally cold (below room temperature) and translationally hot. As the collision energy increases, the DCl product translational energy increases dramatically, the rotational energy increases slightly, and the vibrational energy remains essentially the same. Most of the initial translational collision energy appears as translational energy of the reaction products, and this observation can be simply explained as being a result of the heavy-light-heavy atom reaction kinematics. An extremely simple spectator model, where C6D11 is the spectator, fits this experimental result very well. The cold DCl rotational state distribution may be an indication that Cl atoms abstract D atoms with a collinear C-D-Cl recoil geometry. Quasi-classical trajectory calculations using an empirical three-body model LEPS surface (C6D11 is considered as a structureless particle) successfully predict a number of the experimental results.
Reaction pathways involved in the quenching of the photoactivated aromatic ketones xanthone and 1-azaxanthone by polyalkylbenzenes
Coenjarts,Scaiano
, p. 3635 - 3641 (2007/10/03)
The reactions of the photoexcited aromatic ketones, xanthone and 1-azaxanthone, with polyalkylbenzene donors yields the corresponding ketyl radicals as detected by nanosecond laser flash photolysis. On the basis of formation of these photoreduced products, the quenching of the photoexcited species is expected to occur either by a one-step hydrogen abstraction from the donor, electron transfer followed by proton transfer from the donor, or by formation of a charge-transfer type encounter complex prior to hydrogen atom transfer. The reactions of triplet xanthone and triplet 1-azaxanthone with polyalkylbenzene donors in acetonitrile were investigated to probe the effect of the nature of the triplet state and the redox properties on the relative importance of each quenching pathway. Determination of bimolecular rate constants, as well as analysis of kinetic isotope effects and ketyl radical yields, suggests that for both xanthone and 1-azaxanthone the quenching process is dominated by formation of charge-transfer encounter complexes between excited-state aromatic ketone acceptor and ground-state polyalkylbenzene donor. The reactivites of the xanthone π,π* triplet and 1-azaxanthone n,π* triplet toward these donors is shown to be governed by their reduction potentials, with their electronic configuration being unimportant to the kinetics of encounter complex formation. The only exception to this is found when sterically encumbered polyalkylbenzene donors are employed. Results with these compounds suggest that π,π* and n,π* states form encounter complexes of different structure which affects their ability to react with hindered donors. Additionally, product yields with all of the donors are controlled by both the extent of charge transfer within encounter complexes and the encounter complex structure.
