Formation of stoichiometrically O-18-labelled oxygen from the oxidation of O-18-enriched water mediated by a dinuclear manganese complex: a mass spectrometry and EPR study
2008 (English)In: Energy & Environmental Science, ISSN 1754-5692, E-ISSN 1754-5706, Vol. 1, no 6, 668-676 p.Article in journal (Refereed) Published
Oxygen formation was detected for the oxidations of various multinuclear manganese complexes by oxone (HSO5-) in aqueous solution. To determine to what extent water was the source of the evolved O-2, (H2O)-O-18 isotope-labelling experiments coupled with membrane inlet mass spectrometry (MIMS) were carried out. We discovered that during the reaction of oxone with [Mn-2(OAc)(2)(bpmp)](+) (1), stoichiometrically labelled oxygen (O-18(2)) was formed. This is the first example of a homogeneous reaction mediated by a synthetic manganese complex where the addition of a strong chemical oxidant yields O-18(2) with labelling percentages matching the theoretically expected values for the case of both O-atoms originating from water. Experiments using lead acetate as an alternative oxidant supported this finding. A detailed investigation of the reaction by EPR spectroscopy, MIMS and Clark-type oxygen detection enabled us to propose potential reaction pathways.
Place, publisher, year, edition, pages
2008. Vol. 1, no 6, 668-676 p.
IdentifiersURN: urn:nbn:se:uu:diva-108518DOI: 10.1039/b811806jISI: 000263888600006ISBN: 1754-5692OAI: oai:DiVA.org:uu-108518DiVA: diva2:236170