Oxidation of the perchlorotriphenylmethyl radical to the carbocation, and its unique abrupt reversion.
A solution of AlCl(3) in CH(2)Cl(2) reacts slowly, at room temperature, with perchlorotriphenylmethyl radical (PTM(*)), an inert carbon free radical, to give perchlorotriphenylmethyl cation (PTM(+)) quantitatively. However, by gradual addition of CH(2)Cl(2) into the resulting solution a point is reached where the PTM(+) reverts to PTM(*) instantaneously and quantitatively. A mechanism for this exceptional phenomenon is suggested. Some PTM(+) reactions, namely hydrolysis yielding quinonoid species and single-electron transfers with hydride ion donors, are reported and discussed.
Ballester
Manuel
M
Institut de Ciència de Materials de Barcelona, C.S.I.C., Campus Universitari de Bellaterra, 08193 Cerdanyola, Spain. elies.molins@icmab.es
Miravitlles
Carlos
C
Molins
Elies
E
Carreras
Conxita
C