Kinetics and mechanisms of oxygen transfer in the reaction of p-cyano-N,N-dimethylaniline N-oxide with metalloporphyrin salts. 4. Catalysis by meso-(tetrakis(2,6-dimethylphenyl)porphinato)iron(III) chloride

Journal Article · Wed Dec 10 04:00:00 EST 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00285a018· OSTI ID:7032992

Woon, T C; Dicken, C M; Bruice, T C

meso-(Tetrakis(2,6-dimethylphenyl)porphinato)iron(III) chloride (Me/sub 8/ TPP)Fe/sup III/Cl) is a catalyst for the conversion of p-cyano-N,N-dimethylaniline N-oxide (NO) to p-cyano-N,N-dimethylaniline (DA), p-cyano-N-methylaniline (MA), p-cyano-N-formyl-N-methylaniline (FA), p-cyanoaniline (A), N,N'-dimethyl-N,N'-bis(p-cyanophenyl)hydrazine (H), N,N'-bis(p-cyanophenyl)-N-methylmethylenediamine (MD), and CH/sub 2/O. All evidence supports these reactions to occur by equilibrium ligation of NO to iron(III) porphyrin followed by rate-determining oxygen transfer to yield as immediate products DA and the iron(IV)-oxo porphyrin ..pi..-cation radical. Stepwise oxidation of DA by the higher valent iron-oxo porphyrin species is responsible for the formation of the other products (i.e., DA ..-->.. ..-->.. FA, DA ..-->.. MA ..-->.. A, 2MA ..-->.. MD, and 2MA ..-->.. H). The oxidation potentials of (Me/sub 8/TPP)Fe/sup III/OCH/sub 3/ are comparable to those of the unsubstituted meso-(tetraphenyl-porphinato)iron(III) methoxide ((TPP)Fe/sup III/OCH/sub 3/). The following results are, therefore, not surprising: (i) the second-order rate constant (k/sub a/k/sub b//k/sub -a/) for reaction of Me/sub 8/TPP)Fe/sup III/Cl with NO is but 3.3-fold smaller than in the case of the reaction of NO with (TPP)Fe/sup III/Cl; (ii) the percentage yields of products (DA, 53%; MA, 24%; A, 3%; FA, 8%; H, 7%; MD, 5%) are comparable to when (TPP)Fe/sup III/Cl is employed; and (iii) oxidation and epoxidation of added substrates are not rate-determining.

• Research Organization: Univ. of California, Santa Barbara
• OSTI ID: 7032992
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:25; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AMINES
ANILINE
AROMATICS
CARBONIC ACID DERIVATIVES
CARBOXYLIC ACIDS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CYANATES
DATA
ELEMENTS
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
IRON COMPOUNDS
KINETICS
MANGANESE COMPOUNDS
NITROGEN COMPOUNDS
NONMETALS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN
OXYGEN COMPOUNDS
PORPHYRINS
REACTION KINETICS
TRANSITION ELEMENT COMPOUNDS
YIELDS