Oxo vs Imido Alkylidene d⁰‑Metal Species: How and Why Do They Differ in Structure, Activity, and Efficiency in Alkene Metathesis?

Density functional calculations have been carried out to analyze the origin of the differences in reactivity, selectivity, and stability toward deactivation in metathesis of d⁰ oxo alkylidene complexes vs their isoelectronic imido counterparts. DFT calculations show that the elementary steps and geometries of the extrema are similar for the oxo and imido complexes, but that the energy profiles are different, the greatest difference occurring for the deactivation pathway. For the alkene metathesis pathway, replacing the imido by an oxo ligand slightly lowers the energy barrier for alkene coordination but raises that for the [2+2]-cycloaddition and cycloreversion; it also destabilizes the trigonal bipyramidal (<b>TBP</b>) metallacyclobutane intermediate with respect to the separated reactants. The isomeric square-based pyramid (<b>SP</b>) metallacyclobutane is in general more stable, and its stability relative to the separated reactants is similar for oxo and imido systems. Consequently, the oxo complex is associated with a slightly larger energy difference between the lowest energy intermediate (<b>SP</b> or separated reactants) and the highest energy transition state (cycloreversion) than the imido complex, which accounts for a slightly lower activity. Changing the imido into an oxo ligand disfavors strongly the deactivation pathway by raising considerably the energy barrier of the β-H transfer at the <b>SP</b> metallacycle that begins the entry into the channel for deactivation and byproduct formation as well as that of the subsequent ethene insertion. This makes the oxo catalysts more selective and stable toward deactivation than the corresponding imido catalysts, when dimerization can be avoided