KINETIC DEUTERIUM-ISOTOPE EFFECT PROFILES AND SUBSTITUENT EFFECTS IN THE OXIDATIVE N-DEMETHYLATION OF N,N-DIMETHYLANILINES CATALYZED BY TETRAKIS(PENTAFLUOROPHENYL)PORPHYRIN IRON(III) CHLORIDE
E. Baciocchi et al., KINETIC DEUTERIUM-ISOTOPE EFFECT PROFILES AND SUBSTITUENT EFFECTS IN THE OXIDATIVE N-DEMETHYLATION OF N,N-DIMETHYLANILINES CATALYZED BY TETRAKIS(PENTAFLUOROPHENYL)PORPHYRIN IRON(III) CHLORIDE, Journal of the American Chemical Society, 120(23), 1998, pp. 5783-5787
The mechanistic dichotomy (hydrogen atom transfer or electron-transfer
mechanism) in the oxidative N-dealkylation of a series 4-X-N,N-dimeth
ylanilines (X = MeO, Me, H, Br, CF3, CN, NO2) by PhIO, catalyzed by te
trakis(pentafluorophenyl)porphyrin iron(LII) chloride (FeTPFPPCl), was
investigated in CH2Cl2 by determining both the intra- and the intermo
lecular kinetic deuterium isotope effects and the effect of substituen
ts on reactivity. The results were as follows: (a) The values of k(H)/
k(D)(intra), obtained by the study of 4-X-N-methyl-N-trideuteriomethyl
anilines [2.0 (X = NO2), 2.0 (X = CN), 2.6 (X = Br), 3.1 (X = H), 3.2
(X = Me), 3.3 (X MeO)], regularly decreased on going from electron don
ating to electron withdrawing substituents, a trend exactly contrary t
o that found for the hydrogen atom transfer reactions of some of the s
ame substrates with tert-butoxyl radicals. (b) The intermolecular kine
tic deuterium isotope effects, k(H)/k(D)(inter), determined by competi
tive experiments with 4-X-substituted N,N-dimethyl- and N,N-bis(trideu
teriomethyl)anilines [k(H)/k(D)(inter) for X H, Br, and MeO, 1.6, 1.5
and 1.9, respectively], were significantly different from the correspo
nding k(H)/k(D)(intra) values. (c) The relative reactivities of 4-X-su
bstituted N,N-dimethylanilines, determined by competitive kinetics, sp
anned a reactivity range of 25 (from X = NO2 to X = MeO) and were nice
ly correlated by the substituent constants sigma(+). A rho value of -0
.88 (r(2) = 0.98) was determined by this correlation. The relative rea
ctivity can also be fitted to the Rehm-Welter equation for electron-tr
ansfer reactions. A value of 47 kcal mol(-1) for the reorganization en
ergy was calculated. Altogether, the above results, and particularly p
oints (a) and (b), allow us to dismiss the operation of a hydrogen ato
m transfer mechanism. A one electron transfer mechanism is instead con
sistent with these results and appears therefore the most likely pathw
ay for the oxidative N-demethylation of N,N-dimethylanilines catalyzed
by iron porphyrins. The intramolecular kinetic deuterium isotope effe
ct profile is a useful tool for distinguishing electron transfer from
hydrogen atom transfer mechanisms.