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

Richard A J O'Hair; Valentino Canale; Athanasios Zavras; George N Khairallah; Nicola d'Alessandro

doi:10.1255/ejms.1332

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

Eur J Mass Spectrom (Chichester). 2015;21(3):557-68. doi: 10.1255/ejms.1332.

Authors

Richard A J O'Hair¹, Valentino Canale², Athanasios Zavras³, George N Khairallah⁴, Nicola d'Alessandro⁵

Affiliations

¹ School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, University of Melbourne, 30 Flemington Rd, Parkville, Victoria 3010, Australia. ARC Centre of Excellence for Free Radical Chemistry and Biotechnology. rohair@unimelb.edu.au.
² School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, University of Melbourne, 30 Flemington Rd, Parkville, Victoria 3010, Australia. ARC Centre of Excellence for Free Radical Chemistry and Biotechnology. Department of Engineering and Geology (INGEO), "G. d'Annunzio" University of Chieti and Pescara, Viale Pindaro, 42, I- 65127 Pescara, Italy. valentino.canale@libero.it.
³ School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, University of Melbourne, 30 Flemington Rd, Parkville, Victoria 3010, Australia. ARC Centre of Excellence for Free Radical Chemistry and Biotechnology. az2256@mail.cumc.columbia.edu.
⁴ School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, University of Melbourne, 30 Flemington Rd, Parkville, Victoria 3010, Australia. ARC Centre of Excellence for Free Radical Chemistry and Biotechnology. gkhai@unimelb.edu.au.
⁵ Department of Engineering and Geology (INGEO), "G. d'Annunzio" University of Chieti and Pescara, Viale Pindaro, 42, I- 65127 Pescara, Italy. dalessan@unich.it.

PMID: 26307735
DOI: 10.1255/ejms.1332

Abstract

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 [ReO(2)](-) 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 [ReO(2)(CH(2)CO(2))](-) (m/z 277) and H(2); [CH(3)ReO(2)(OH)](-) (m/z 251) and CO; and [ReO(3)](-) (m/z 235), H(2) and CH(2)CO.