A broadly tunable synthesis of linear α-olefins.

The catalytic synthesis of linear α-olefins from ethylene is a technologically highly important reaction. A synthesis concept allowing the formation of selective products and various linear α-olefin product distributions with one catalyst system is highly desirable. Here, we describe a trimetallic catalyst system (Y-Al-Ni) consisting of a rare earth metal polymerization catalyst which can mediate coordinative chain transfer to triethylaluminum combined with a simultaneously operating nickel β-hydride elimination/transfer catalyst. This nickel catalyst displaces the grown alkyl chains forming linear α-olefins and recycles the aluminum-based chain transfer agent. With one catalyst system, we can synthesize product spectra ranging from selective 1-butene formation to α-olefin distributions centered at 850 gmol-1 with a low polydispersity. The key to this highly flexible linear α-olefin synthesis is the easy tuning of the rates of the Y and Ni catalysis independently of each other. The reaction is substoichiometric or formally catalytic regarding the chain transfer agent.