Enhanced activity and selectivity in cyclohexane autoxidation by inert H-bond acceptor catalysts

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
Ive HermansPierre A Jacobs

Abstract

Herein, we demonstrate that the chain-initiating dissociation of cyclohexyl hydroperoxide, CyOOH, is substantially accelerated by H-bond acceptors (e.g. Teflon), which assist O-O bond breaking by stabilising the leaving *OH radical. This is a completely new approach to boost the chain-propagating radical concentration. Indeed, up to now, literature has remained focussed on transition metal catalysis. In addition to this initiation effect, we demonstrate how inert perfluorinated compounds are also able to steer the selectivity at the molecular level, by promoting the conversion of the intermediate cyclohexyl hydroperoxide to the most desired end-product, cyclohexanone. This effect is explained by an enhanced, H-bond-assisted, hydroperoxide propagation. This hitherto overlooked hydroperoxide propagation was recently presented by us as the dominant cyclohexanone and cyclohexanol source. We herein thus confirm our previously reported autoxidation scheme, and illustrate its usefulness as a solid basis for designing new catalytic systems.

References

May 11, 2005·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Ive HermansJozef Peeters
Dec 27, 2005·The Journal of Physical Chemistry. B·Peter VassilevEvert Jan Baerends
Jul 13, 2006·The Journal of Physical Chemistry. a·Julia M Khalack, Alexander P Lyubartsev
Apr 7, 2005·Physical Chemistry Chemical Physics : PCCP·Joost VandeVondele, Michiel Sprik

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Citations

Dec 13, 2006·Chemistry : a European Journal·Ive HermansJozef Peeters
Oct 17, 2006·Angewandte Chemie·Eric BreynaertPierre Jacobs
Apr 19, 2006·Chemistry : a European Journal·Ive HermansJozef Peeters
Nov 30, 2012·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Kexian ChenHaoran Li
Mar 13, 2014·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Kexian ChenHaoran Li
Sep 27, 2014·Physical Chemistry Chemical Physics : PCCP·Xi LiuMarco Conte
Mar 16, 2017·Chemistry : a European Journal·Xi LiuGraham J Hutchings

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