Metathetic Oxidation of 2-Butenes to Acetaldehyde by Molecular Oxygen Using the Single-Site Olefin Metathesis Catalyst ( SiO)(2)Mo(=O)(2)

摘要

The catalytic oxidation of cis-2-butene and propylene with molecular oxygen in the presence of a well-defined surface coordination compound, ( SiO)(2)Mo(=O)(2), affords acetaldehyde. Using a cis-2-butene/O-2 feed at 350-400 degrees C, the reaction yields a conversion of approximately 10% and an acetaldehyde selectivity of approximately 70%. This performance is maintained up to an experimental time of 20 h in a continuous flow reactor. The Mo(bis-oxo) surface compound was fully characterized by multiple spectroscopic techniques as well as surface microanalysis. The results from quantum mechanics calculations indicate that the reaction proceeds via [2 + 2] cycloaddition/cycloelimination steps with the formation of metalla-oxacyclobutane intermediates, analogous to the Chauvin mechanism in olefin metathesis.