Decarboxylation versus Acetonitrile Loss in Silver Acetate and Silver Propiolate Complexes, [RCO2Ag2(CH3CN)n] (where R = CH3 and CH3C≡C; N = 1 and 2)

Abstract

Gas-phase experiments using collision-induced dissociation in an ion trap mass spectrometer have been used in combination with density functional theory (DFT) calculations (at the B3LYP/SDD6-31+G(d) level of theory) to examine the competition between decarboxylation and loss of a coordinated acetonitrile in the unimolecular fragmentation reactions of the silver acetate and silver propiolate complexes, [RCO2Ag2(CH3CN)n]+ (where R=CH3 and CH3C≡C; n=1 and 2), introduced into the gas-phase via electrospray ionisation. When R=CH3, loss of acetonitrile is the sole reaction channel observed for both complexes (n=1 and 2), consistent with DFT calculations, which highlight that the barriers for decar..