Density Functional Theory Study of the Reaction between d⁰ Tungsten Alkylidyne Complexes and H₂O: Addition versus Hydrolysis

The reactions of early-transition-metal complexes with H₂O have been investigated. An understanding of these elementary steps promotes the design of precursors for the preparation of metal oxide materials or supported heterogeneous catalysts. Density functional theory (DFT) calculations have been conducted to investigate two elementary steps of the reactions between tungsten alkylidyne complexes and H₂O, i.e., the addition of H₂O to the W≡C bond and ligand hydrolysis. Four tungsten alkylidyne complexes, W(≡CSiMe₃)(CH₂SiMe₃)₃ (A-1), W(≡CSiMe₃)(CH₂ ^tBu)₃ (B-1), W(≡C^tBu)(CH₂ ^tBu)₃ (C-1), and W(≡C^tBu)(O^tBu)₃ (D-1), have been compared. The DFT studies provide an energy profile of the two competing pathways. An additional H₂O molecule can serve as a proton shuttle, accelerating the H₂O addition reaction. The effect of atoms at the α and β positions has also been examined. Because the lone-pair electrons of an O atom at the α position can interact with the orbital of the proton, the barrier of the ligand-hydrolysis reaction for D-1 is dramatically reduced. Both the electronic and steric effects of the silyl group at the β position lower the barriers of both the H₂O addition and ligand-hydrolysis reactions. These new mechanistic findings may lead to the further development of metal complex precursors.