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Magnetic field effects on the Mn(5NO/sub 2/SMDPT)-catalyzed oxidation of 2,6-di-tert-butylphenol: /sup 2/H and /sup 17/O magnetic isotope effects

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00280a037· OSTI ID:5614249

The effect of a magnetic field between 0 and 70 kG on the rate of catalytic oxidation of 2,6-di-tert-butylphenol (DTBP) to form 2,2',6,'-tetra-tert-butyldiphenoquinone (DPQ) by (bis(3-((5-nitrosalicylidene)amino)propyl)methylaminato)manganese(II) (Mn(5NO/sub 2/SMDPT)) in the presence of O/sub 2/ is reported. No kinetic /sup 2/H isotope effect is observed with DTBP-O-d, and DTBP-4,O-d/sub 2/ exhibits mass and magnetic kinetic isotope effects of 1.46 and 1.23, respectively. No /sup 17/O kinetic isotope effect is observed for isotopically enriched O/sub 2/. These results are compared to the rate of oxidation of DTBP-4,O-d/sub 2/ exhibits a /sup 2/H kinetic isotope effect of 1.28. The rate of oxidation of the proposed intermediate 4,4'-dihydroxy-3,3',5,5'-tetra-tert-butylbiphenyl (TTBBP) by Mn(5NO/sub 2/SMDPT) or Pb(OAc)/sub 4/ gives a maximum rate relative to zero magnetic field of 1.09 /plus minus/ 0.06 or 1.02 /plus minus/ 0.07, respectively. These results are discussed in terms of a proposed mechanism. 22 refs., 2 figs., 2 tabs.

Research Organization:
Tufts Univ., Medford, MA (USA)
OSTI ID:
5614249
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:7; ISSN INOCA
Country of Publication:
United States
Language:
English