Shape Selective Oxidations of Hydrocarbons

Tetrakis-5,10,15,20-(2',4',6'-triphenylphenyl)porphyrinate (TTPPP) manganese(III) and iron(III) acetate were both found to be shape selective alkane hydroxylation catalysts when iodosobenzene was used as oxidant. The selectivity observed was the same when these catalysts were used with metachloroperoxybenzoic acid, demonstrating the intermediacy of a common manganese porphyrin based oxidant. Primary selectivity was found to be diminished for FeTTPPP(OAc) relative to MnTTPPP(OAc), consistent with a greater amount of C-H bond breaking in the iron transition state. Shape selectivity was used as a sensitive probe for metalloporphyrin involvement in the hydroxylation transition state. Both tert-butylhydroperoxide and trifluoroethanol solubilized pentafluoroiodosobenzene were found not to be shape selective with manganese porphyrin catalysts indicating radical chain oxidation.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Cook, Bruce Randall

• Chemistry, Inorganic

Identifier

(UMI)AAI8711785

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70360