Magnetic field effects on the catalytic oxidation of 2,6-Di-tert-butylphenol by CoSMDPT: /sup 2/H and /sup 17/O magnetic isotope effects

Journal Article · Wed May 25 00:00:00 EDT 1988 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00219a022· OSTI ID:7200439

Perito, R P; Corden, B B

The effect of a magnetic field between 0 and 70 kG on the catalytic oxidation rate of 2,6-di-tert-butylphenol, DTBP, to form 2,6-di-tert-butylquinone, BQ, by cobalt(II) bis(3-(salicylideneamino)propyl)methylamine, CoSMDPT, in the presence of O/sub 2/ is reported. No kinetic /sup 2/H isotope effect is observed with DTBP-OD, and DTBP-4-d/sub 1/-OD exhibits mass and magnetic kinetic isotope effects of 1.25 and 1.22, respectively. In the presence of additive phenol, CoSMDPT catalyzes the formation of 2,2',6,6'-tetra-tert-butyldiphenoquinone, DPQ. The mass and magnetic isotope effects in DPQ formation are negligible for the deuteriation of the phenolic position. DTBP-4-d/sub 1/-OD in the presence of phenol-OD exhibits kinetic mass and magnetic /sup 2/H isotope effects in DPQ formation of 1.73 and 1.31, respectively. These results are compared to the oxidation rate of DTBP by Pb(OAc)/sub 4/, which is unaffected by a 0-70-kG magnetic field and has a /sup 2/H kinetic isotope effect of 1.28 for DTBP-4-d/sub 1/-OD. A significant /sup 17/O magnetic isotope effect is observed only for BQ production. The /sup 17/O enrichment of BQ given has an overall enrichment factor, S(f) = 1.76, at 9% DTBP conversion. These results are discussed in terms of a proposed mechanism.

• Research Organization: Tufts Univ., Medford, MA (USA)
• OSTI ID: 7200439
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:11; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AMINES
AROMATICS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPLEXES
DATA
DEUTERIUM
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
MAGNETIC FIELDS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXIDATION
OXYGEN 17
OXYGEN ISOTOPES
PHENOLS
REACTION KINETICS
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES