TY - JOUR
T1 - MIL-101 as reusable solid catalyst for autoxidation of benzylic hydrocarbons in the absence of additional oxidizing reagents
AU - Santiago-Portillo, Andrea
AU - Navalón, Sergio
AU - Cirujano, Francisco G.
AU - Xamena, Francesc X.Llabrés I.
AU - Alvaro, Mercedes
AU - Garcia, Hermenegildo
N1 - Publisher Copyright:
© 2015 American Chemical Society.
Copyright:
Copyright 2015 Elsevier B.V., All rights reserved.
PY - 2015/6/5
Y1 - 2015/6/5
N2 - Materiaux de l'Institute Lavosier-101 (MIL-101) promotes benzylic oxidation of hydrocarbons exclusively by molecular oxygen in the absence of any other oxidizing reagent or initiator. Using indane as model compound, the selectivity toward the wanted ol/one mixture is higher for MIL-101(Cr) (87% selectivity at 30% conversion) than for MIL-101(Fe) (71% selectivity at 30% conversion), a fact that was associated with the preferential adsorption of indane within the pore system. Product distribution and quenching experiments with 2,2,6,6-tetramethyl-1-piperidinyloxy, benzoic acid, and dimethylformamide show that the reaction mechanism is a radical chain autoxidation of the benzylic positions by molecular oxygen, and the differences in selectivity have been attributed to the occurrence of the autoxidation process inside or outside the metal organic framework pores. MIL-101 is reusable, does not leach metals to the solution, and maintains the crystal structure during the reaction. The scope of the benzylic oxidation was expanded to other benzylic compounds including ethylbenzene, n-butylbenzene, iso-butylbenzene, 1-bromo-4-butylbenzene, sec-butylbenzene, and cumene.
AB - Materiaux de l'Institute Lavosier-101 (MIL-101) promotes benzylic oxidation of hydrocarbons exclusively by molecular oxygen in the absence of any other oxidizing reagent or initiator. Using indane as model compound, the selectivity toward the wanted ol/one mixture is higher for MIL-101(Cr) (87% selectivity at 30% conversion) than for MIL-101(Fe) (71% selectivity at 30% conversion), a fact that was associated with the preferential adsorption of indane within the pore system. Product distribution and quenching experiments with 2,2,6,6-tetramethyl-1-piperidinyloxy, benzoic acid, and dimethylformamide show that the reaction mechanism is a radical chain autoxidation of the benzylic positions by molecular oxygen, and the differences in selectivity have been attributed to the occurrence of the autoxidation process inside or outside the metal organic framework pores. MIL-101 is reusable, does not leach metals to the solution, and maintains the crystal structure during the reaction. The scope of the benzylic oxidation was expanded to other benzylic compounds including ethylbenzene, n-butylbenzene, iso-butylbenzene, 1-bromo-4-butylbenzene, sec-butylbenzene, and cumene.
KW - aerobic oxidation
KW - benzylic oxidation
KW - heterogeneous catalysis
KW - metal organic frameworks
KW - MIL-101 as catalyst
UR - http://www.scopus.com/inward/record.url?scp=84930682941&partnerID=8YFLogxK
U2 - 10.1021/acscatal.5b00411
DO - 10.1021/acscatal.5b00411
M3 - Article
AN - SCOPUS:84930682941
SN - 2155-5435
VL - 5
SP - 3216
EP - 3224
JO - ACS Catalysis
JF - ACS Catalysis
IS - 6
ER -