Jump to main content
Jump to site search

Issue 5, 2016
Previous Article Next Article

Oxidation of olefins with H2O2 catalysed by salts of group III metals (Ga, In, Sc, Y and La): epoxidation versus hydroperoxidation

Author affiliations

Abstract

The catalytic activity of aqua complexes of the group III metals [M(H2O)n]3+ (M = Ga, In, Sc, n = 6; M = Y, n = 8; M = La, n = 9) towards the oxidation of olefins with H2O2 was investigated in detail by theoretical (DFT) methods. It was predicted and then confirmed in a preliminary experiment that these complexes formed from simple soluble salts in aqueous medium are able to efficiently catalyse the olefin oxidation. The reaction occurs via two competitive reaction channels which are realized concurrently, i.e. (i) hydroperoxidation of the allylic C atom(s) via a radical Fenton-like mechanism involving HO˙ radicals and leading to alkyl hydroperoxides ROOH and (ii) epoxidation of the C[double bond, length as m-dash]C bond through a one-step mechanism involving oxygen transfer from the hydroperoxo ligand in an active catalytic form [M(H2O)nk(OOH)]2+ (M = Ga, In, Y, La, k = 2; M = Sc, k = 1) to the olefin molecule and leading to epoxides and/or trans-diols. Other concerted and stepwise mechanisms of the epoxidation were also considered but found less favourable.

Graphical abstract: Oxidation of olefins with H2O2 catalysed by salts of group III metals (Ga, In, Sc, Y and La): epoxidation versus hydroperoxidation

Back to tab navigation

Supplementary files

Publication details

The article was received on 19 Aug 2015, accepted on 18 Sep 2015 and first published on 21 Sep 2015


Article type: Paper
DOI: 10.1039/C5CY01367D
Citation: Catal. Sci. Technol., 2016,6, 1343-1356
  •   Request permissions

    Oxidation of olefins with H2O2 catalysed by salts of group III metals (Ga, In, Sc, Y and La): epoxidation versus hydroperoxidation

    A. S. Novikov, M. L. Kuznetsov, B. G. M. Rocha, A. J. L. Pombeiro and G. B. Shul'pin, Catal. Sci. Technol., 2016, 6, 1343
    DOI: 10.1039/C5CY01367D

Search articles by author

Spotlight

Advertisements