ABSTRACT
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.
ABSTRACT
Gas-phase ion-ion reactions between tris-1,10-phenantholine metal dications, [(phen)3M]2+ (where M = Ni and Mg), and the tetraphenylborate anion yield the ion-pairs {[(phen)3M]2+[BPh4]-}+. The ion-pairs undergo transmetalation upon loss of a phen ligand to give the organometallic complexes [(phen)2M(Ph)]+. DFT calculations, used to determine the energy barriers for the transmetalation reactions and the hydrolysis reactions, are entirely consistent with the experimental results.
