화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.120, No.47, 9363-9369, 2016
Organometallic Chalcones Functioning as Radical Traps: Observations on the Solvated Electron Reduction and the C center dot H2OH and C center dot H2Cl Addition Processes. A Time-Resolved, Mechanistic Study
The pulse radiolysis method was used to investigate reactions between organometallic chalcones derived from ferrocene, cyrhetrene, and cymantrene substituted with a phenyl (R-1) or a 4'-benzo-15-crown-5 (B-1) moiety and the solvated electron e(sol)(-) and two radicals. The principal spectroscopic transformations resolved with the e(sol)(-) reactions reveal that the chalcone compounds react under a diffusion controlled condition. The chromophore in the reaction product is the radical anion chalcone, -C(=O)CH=CH-. The kinetics of the redox processes are consistent with the formation of the radical anion in a first step, followed by an E/Z isomerization reaction in the second step. The rate of the E/Z isomerization reaction is dependent on the chalcone substituent. Reactions with C center dot H2OH and C center dot H2Cl radicals are strongly affected by the nature of the organometallic fragment. The transient spectra for the reactions between C-H2OH and C center dot H2Cl radicals with the phenyl-substituted chalcone show weak, broad absorption bands at lambda(ob) < 400 nm. Only the ferrocenyl derivatives showed an intense absorption band with lambda(max) = 350 nm. The C-centered radicals react with organometallic chalcones with lifetimes less than or equal to a few microseconds, and the products are assigned as adducts of the C-centered radicals to the chalcone.