Formation of stoichiometrically 18O-labelled oxygen from the oxidation of 18O-enriched water mediated by a dinuclear manganese complex-a mass spectrometry and EPR study
2008 (English)In: Energy & Environmental Science, Vol. 1, 668-76 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 O2, H218O isotope-labelling experiments coupled with membrane inlet mass spectrometry (MIMS) were carried out. We discovered that during the reaction of oxone with [Mn2(OAc)2(bpmp)]+ (1), stoichiometrically labelled oxygen (18O2) 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 18O2 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, 668-76 p.
IdentifiersURN: urn:nbn:se:umu:diva-11556DOI: doi:10.1039/b811806jOAI: oai:DiVA.org:umu-11556DiVA: diva2:151227