H2 effect in Cr/PNP-catalyzed ethylene tetramerization: a DFT study

It is well noticed that hydrogen promotes catalyst activity in Cr/PNP-catalyzed ethylene tetramerization, but the mechanism of this boost is unclear. A density functional theory (DFT) study devoted to exploring this effect was conducted, and conformation changes were carefully taken into consideration to build a clear reaction pathway. Three components in the catalytic cycle was examined in detail: the production of 1-hexene from the metallacycloheptane, the production of 1-octene from metallacyclononane, and the formation of active center on the catalyst. The result indicates that the formation of active center on the catalyst becomes more favorable upon imposition of hydrogen, where hydrogen function as a second ligand. This easing effect could be the key factor leading to the outperformed catalyst activity.