Gas-phase reactions of the rhenium oxide anions, [ReOx]- (x = 2 - 4) with the neutral organic substrates methane, ethene, methanol and acetic acid

The ion–molecule reactions of the rhenium oxide anions, [ReOx]– (x = 2–4) with the organic substrates methane, ethene, methanol, and acetic acid have been examined in a linear ion trap mass spectrometer. The only reactivity observed was between [ReO2]– and acetic acid. Isotope-labelled experiments and high-resolution mass spectrometry measurements were used to assign the formulas of the ionic products. Collision-induced dissociation and ion–molecule reactions with acetic acid were used to probe the structures of the mass-selected primary product ions. Density functional theory calculations [PBE0/LanL2DZ6-311+G(d)] were used to suggest possible structures. The three primary product channels observed are likely to arise from the formation of the metallalactone [ReO2(CH2CO2)]– (m/z 277) and H2, [CH3ReO2(OH)]– (m/z 251) and CO, and [ReO3]– (m/z 235), H2 and CH2CO.