Ethylene Dimerization in Metal-Organic Frameworks

Eric Metzger, Dincă Group

The benefits of heterogeneous catalysis for industry and the society at large cannot be
overstated, with approximately 90% of all industrial catalysis being performed with
heterogeneous catalysts. Despite the undeniable operational advantages of heterogeneous
catalysts, several large volume industrial processes involved in the production of commodity
chemicals remain impenetrable to solid catalysts. Among them is the selective dimerization of
ethylene, which requires fine steric and electronic tuning to optimize the production 1-butene.
This talk will describe our efforts to use metal-organic frameworks (MOFs) as catalysts for
ethylene dimerization, leveraging the unique tunability of MOFs to develop the most active and
selective heterogeneous catalysts for ethylene dimerization reported to date. The capacity for
mild cation exchange in the material MFU-4l was utilized to create a well-defined and site-
isolated Ni(II) active site bearing close structural homology to molecular tris-pyrazolylborate
complexes. In the presence of ethylene and methylaluminoxane, the material consumes ethylene
at a rate of 41,500 moles per mole of Ni per hour with a selectivity for 1-butene of up to 96.2%,
exceeding the selectivity reported for the current industrial dimerization process. The uniform
catalytic sites available in MFU-4l provide a unique opportunity to directly study the reaction
mechanism of the heterogeneous catalyst, a problem typically intractable due to the multiplicity
of coordination environments found in many solid catalysts. With a combination of isotopic
labeling studies, mechanistic probes, and DFT calculations, we have demonstrated that Ni-MFU-
4l operates via the Cossee-Arlman mechanism, which has also been implicated in homogeneous
late transition metal catalysts. These studies demonstrate that metal nodes in MOFs mimic
homogeneous catalysts not just functionally, but also mechanistically.