Journal of the American Chemical Society p. 3436 - 3443 (1987)
Update date:2022-08-04
Topics:
Bruice, Thomas C.
Dicken, C. Michael
Balasubramanian, P. N.
Woon, T. C.
Lu, Fu-Lung
The decomposition of p-cyano-N,N-dimethylaniline N-oxide (NO) is catalyzed (CH2Cl2 solvent at 25 deg C) by the SbF6- salt of the C2-capped (meso-tetraphenylporphinato)iron(III) of Baldwin ((TPPC2cap)FeIIISbF6).Since neither NO nor the SbF6- anion can fit under the cap, this result establishes that oxygen transfer from NO to the iron(III) center can occur without the intermediate iron(IV)-oxo porphyrin ?-cation being hexacoordinated.The products of NO decomposition (p-cyano-N,N-dimethylaniline (DA) 68percent, p-cyano-N-methylaniline (MA) 12percent, p-cyanoaniline (A) 1percent, N-formyl-p-cyano-N-methylaniline (FA) 6percent, N,N'-dimethyl-N,N'-bis(p-cyanophenyl)hydrazine (H) 7percent, and CH2O 3percent) account for 100percent of p-cyanodimethylaniline moiety of NO, but ca. 40percent of the oxide oxygen of NO remains unaccounted for by product isolation.This is due to some loss of the catalyst and oxidation of the CH2Cl2 solvent during turnover.Oxidation of solvent results in the gradual exchange of the SbF6- axial ligand for Cl-.Product formation on reaction of NO with (TPPC2cap)FeIIISbF6 can be approximated by the first-order rate law.Since the observed first-order rate constants at a given
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(1987)