Preparation of CH_3TiF and (CH_3)_2TiF_2 from the Reaction of CH_3F with Laser-Ablated Ti Atoms

摘要

Laser-ablated Ti atoms react with CH_3F upon condensation with excess argon to form primarily CH_3TiF and (CH_3)_2-TiF_2.Irradiation in the UV region promotes a-hydrogen rearrangement of CH_3TiF to CH_2=TiHF and increases the yield of (CH_3))_2TiF_2.Annealing to allow diffusion and reaction of more CH_3F markedly increases the yield of (CH_3)_2-TiF_2.This shows that the CH_3TiF + CH_3F reaction is spontaneous and that triplet state CH_3TiF is an extremely reactive molecule.B3LYP calculations are extremely effective in predicting vibrational frequencies and isotopic shifts for CH_3TiF and (CH_3)_2TiF_2 and thus in confirming their identification from matrix infrared spectroscopy.