Laser-ablated Ti atoms react with CH3F upon condensation with excess argon to form primarily CH3TiF and (CH3)(2)-TiF2. Irradiation in the UV region promotes alpha-hydrogen rearrangement of CH3TiF to CH2=TiHF and increases the yield of (CH3)(2)TiF2. Annealing to allow diffusion and reaction of more CH3F markedly increases the yield of (CH3)(2)-TiF2. This shows that the CH3TiF + CH3F reaction is spontaneous and that triplet state CH3TiF is an extremely reactive molecule. B3LYP calculations are extremely effective in predicting vibrational frequencies and isotopic shifts for CH3TiF and (CH3)(2)TiF2 and thus in confirming their identification from matrix infrared spectroscopy.