Redox and spin-trapping properties of phosphoryldithioacetates.
The redox properties of ethyl diethoxyphosphoryldithioacetate (1), methyl diethoxyphosphorylfluorodithioacetate (2) and methyl diethoxyphosphoryldifluorodithioacetate (3) were measured by cyclic voltammetry. Addition of free radicals to the three dithioesters led to the detection of the ESR spectra of the spin adducts only with the last two compounds. Based on the reduction potentials of the three dithioacetates, this may be explained by capto-dative stabilization of the adducts. On the basis of DFT calculations, the temperature dependent variations of the spectral patterns exhibited by the radicals were attributed to restricted rotation about the Calpha-SMe bond.
Alberti
Angelo
A
ISOF-CNR, Area della Ricerca di Bologna, Via P. Gobetti 101, 40129 Bologna, Italy. aalberti@isof.cnr.it
Guerra
Maurizio
M
Hapiot
Philippe
P
Lequeux
Thierry
T
Macciantelli
Dante
D
Masson
Serge
S
D004578:Electron Spin Resonance Spectroscopy / Q000379:methods; D007700:Kinetics; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010758:Phosphorus; D010782:Photolysis; D019097:Spin Trapping / Q000379:methods; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D013438:Sulfhydryl Compounds; D010758:Phosphorus; C005732:thioacetic acid