posted on 2024-02-27, 03:03authored byAsma M.
O. Aldajani, Howard Z. Ma, Yang Yang, Allan J. Canty, Richard A. J. O’Hair
Analytes are sampled from both solution phase and gas-phase
environments
during the ESI process, and thus, the mass spectrum that is measured
can reflect both solution and gas-phase conditions. In the gas-phase
regime, ion–molecule reactions can influence the types of
ions that are observed. Herein, the synergistic effects of a Lewis
acid (Mg2+) and background water are shown to lead to protonolysis
of two of the B–C bonds of the tetraphenylborate ion in the
gas phase, giving rise to different ions at different reaction times
in ESI-MS/MS experiments in a linear ion trap mass spectrometer. At
short reaction times (1 ms), the expected adduct [Mg(BPh4)]+ is observed. At 10 ms, [(HO)Mg(BPh3)]+ and [(HO)2Mg(BPh2)]+ are
observed. At 100 ms, the water adducts [(HO)2Mg(BPh2)(H2O)]+ and [(HO)2Mg(BPh2)(H2O)2]+ appear, and these
become the dominant ions at longer reaction times. DFT calculations
provide a plausible explanation as to why only [(HO)Mg(BPh3)]+ and [(HO)2Mg(BPh2)]+ but not [(HO)3Mg(BPh)]+ are observed.