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Manganese 1,4,7-trimethyl-1,4,7-triazacyclononane complexes: Versatile catalysts for the oxidation of organic compounds with hydrogen peroxide

Smith, J.R.L., Gilbert, B.C., Mairata i Payeras, A., Murray, J., Lowdon, T.R., Oakes, J., Pons i Prats, R. and Walton, P.H. (2006) Manganese 1,4,7-trimethyl-1,4,7-triazacyclononane complexes: Versatile catalysts for the oxidation of organic compounds with hydrogen peroxide. Journal of Molecular Catalysis, 251 (251). pp. 114-122. ISSN 1381-1169

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Abstract

The oxidation of phenols, cinnamic acids and methyl aryl sulfides by hydrogen peroxide, using three catalyst systems, [L2Mn2IV(μ-O)3](PF6)2, L = 1,4,7-trimethyl-1,4,7-triazacyclononane; [LMnIV(OMe)3(PF6); and MnII/L/H2O2, have been studied. The results from a combination of spectroscopic and kinetic studies, coupled with Hammett correlations and 18O labelling experiments, suggest that with each system the active oxidant is an electrophilic, mononuclear oxo-manganese (V) species. The influence of additives that can act as co-ligands for the manganese species has been investigated, with a view to controlling the activity/selectivity of the active oxidant. The two-step, sulfide–sulfoxide–sulfone, oxidation shows an unusual switch in the philicity of the active oxidant from electrophilic in the first step to nucleophilic in the second. Mechanisms for the oxidations are proposed.

Item Type: Article
Academic Units: The University of York > Chemistry (York)
Depositing User: York RAE Import
Date Deposited: 01 Jun 2009 12:04
Last Modified: 06 Aug 2009 16:00
Published Version: http://dx.doi.org/10.1016/j.molcata.2006.02.025
Status: Published
Publisher: Elsevier
Refereed: Yes
Identification Number: 10.1016/j.molcata.2006.02.025
URI: http://eprints.whiterose.ac.uk/id/eprint/6766

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