Methyl and methane elimination in the gas phase reaction of zirconium atom with 2-butyne: A DFT study

The mechanisms for CH3- and CH4-elimination in the gas phase reaction of ground-state Zr with 2-butyne has been investigated in detail using B3LYP method. For the elimination of CH3, two mechanisms which are similar to those previously found for the reactions of Y and Zr with propyne are identified. The mechanism for the elimination of CH4 was revealed as: Zr + CH3CCCH3 → π-complex → TS (H-migration) → HZr-(H2CCC)-CH3 → TS(C-C insertion) → (H2CCC)-HZr-CH3 → TS (H-migration) → CH4 + ZrC3H2.