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

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.