The Magnesium Dication and Water Synergistically Promote the Protonolysis of Two of the B-C Bonds in the Tetraphenylborate Anion.

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 (Mg) 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.

Ion-pairs as a gateway to transmetalation: aryl transfer from boron to nickel and magnesium.

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