HOW DO ELECTRONEGATIVE SUBSTITUENTS MAKE METAL-COMPLEXES BETTER CATALYSTS FOR THE OXIDATION OF HYDROCARBONS BY DIOXYGEN

Authors
BOTTCHER A BIRNBAUM ER DAY MW GRAY HB GRINSTAFF MW LABINGER JA
Citation
A. Bottcher et al., HOW DO ELECTRONEGATIVE SUBSTITUENTS MAKE METAL-COMPLEXES BETTER CATALYSTS FOR THE OXIDATION OF HYDROCARBONS BY DIOXYGEN, Journal of molecular catalysis. A, Chemical, 117(1-3), 1997, pp. 229-242
Citations number
36
Categorie Soggetti
Chemistry Physical
Journal title
Journal of molecular catalysis. A, Chemical → ACNP
ISSN journal
13811169
Volume
117
Issue
1-3
Year of publication
1997
Pages
229 - 242
Database
ISI
SICI code
1381-1169(1997)117:1-3<229:HDESMM>2.0.ZU;2-F
Abstract
Modeling studies support a radical-chain autoxidation mechanism for th e aerobic oxidation of isobutane catalyzed by halogenated porphyrin ir on complexes. A key role of the electronegative halogen substituents i s to increase the Fe-III/(II) redox potential and thereby accelerate o xidation of the intermediate t-butyl hydroperoxide by (porph)Fe-III. T he electronic structures of electronegatively substituted salen iron c omplexes have been characterized by several techniques, and related to changes in catalytic activity for oxidation of cyclohexene. The cryst al and molecular structure of [Fe((NO2)(4)salen)(H2O)Cl] is reported.