Activities of polyhedral vanadium-containing silsequioxane-based catalysts for photo-assisted oxidation of hydrocarbons

Activities of polyhedral vanadium-containing silsequioxane-based catalysts for photo-assisted... The catalytic activity of a polyhedral vanadium-containing silsesquioxane ((c-C5H9)7Si7O12VO, 1b) with a cubic core structure towards the selective photooxidation of benzene, cyclohexane, and adamantane was examined under O2 (1 atm) at around 300 K. The reaction of benzene in the presence of 1b afforded phenol selectively, but the TON was low (≈1.4). Complex 1b showed high activity towards the reaction of cyclohexane (TON ≈16) and adamantane (TON≈7.0). The order of the reactivity of the C−H bonds in adamantane was tertiary C−H> secondary C−H. In addition to 1b, the mixtures of vanadyl bisacetylacetonate and incompletely-condensed silsesquioxanes with silanol functionality showed relatively high activities, although vanadyl bisacetylacetonate itself was not effective. The degradation of the catalysts in the course of the reaction was partly suppressed in the presence of molecular sieves-4A. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Activities of polyhedral vanadium-containing silsequioxane-based catalysts for photo-assisted oxidation of hydrocarbons

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Publisher
Springer Netherlands
Copyright
Copyright © 1998 by Springer
Subject
Chemistry; Catalysis; Physical Chemistry; Inorganic Chemistry
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1163/156856798X00041
Publisher site
See Article on Publisher Site

Abstract

The catalytic activity of a polyhedral vanadium-containing silsesquioxane ((c-C5H9)7Si7O12VO, 1b) with a cubic core structure towards the selective photooxidation of benzene, cyclohexane, and adamantane was examined under O2 (1 atm) at around 300 K. The reaction of benzene in the presence of 1b afforded phenol selectively, but the TON was low (≈1.4). Complex 1b showed high activity towards the reaction of cyclohexane (TON ≈16) and adamantane (TON≈7.0). The order of the reactivity of the C−H bonds in adamantane was tertiary C−H> secondary C−H. In addition to 1b, the mixtures of vanadyl bisacetylacetonate and incompletely-condensed silsesquioxanes with silanol functionality showed relatively high activities, although vanadyl bisacetylacetonate itself was not effective. The degradation of the catalysts in the course of the reaction was partly suppressed in the presence of molecular sieves-4A.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Apr 15, 2009

References

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