Smith, J.R.L., Gilbert, B.C., Mairata i Payeras, A. et al. (5 more authors) (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
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.
|Institution:||The University of York|
|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|