Gas-phase ion chemistry of BF3/CH4 mixtures: Activation of methane by ions

The gas-phase ion chemistry of BF3/CH4 mixtures was investigated by the joint application of mass-spectrometric and ab initio theoretical methods. The addition of BF 2 + to CH4 led to the observation of BF 2 CH 4 + and BFCH 3 + ions in the gas phase. Collisionally activated dissociation (CAD) mass-spectrometric results and theoretical calculations performed at the B3LYP and CCSD(T) levels identified the F 2 B – CH 4 + and F – B – CH 3 + ions as the most stable isomers on the [BFnCHn+2]+ (n = 1, 2) potential energy surfaces. It is worth noting that C–N bond formation was observed when BFCH 3 + ions were allowed to react with NH3.