Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst

Current heterogeneous catalysts lack the fine steric and electronic tuning required for catalyzing the selective dimerization of ethylene to 1-butene, which remains one of the largest industrial processes still catalyzed by homogeneous catalysts. Here, we report that a metal–organic framework cataly...

Full description

Bibliographic Details
Main Authors: Metzger, Eric Daniel, Brozek, Carl Kavanaugh, Comito, Robert J, Dinca, Mircea
Other Authors: Massachusetts Institute of Technology. Department of Chemistry
Format: Article
Language:en_US
Published: American Chemical Society (ACS) 2017
Online Access:http://hdl.handle.net/1721.1/110550
https://orcid.org/0000-0001-6597-1981
https://orcid.org/0000-0003-1298-2876
https://orcid.org/0000-0002-1262-1264
Description
Summary:Current heterogeneous catalysts lack the fine steric and electronic tuning required for catalyzing the selective dimerization of ethylene to 1-butene, which remains one of the largest industrial processes still catalyzed by homogeneous catalysts. Here, we report that a metal–organic framework catalyzes ethylene dimerization with a combination of activity and selectivity for 1-butene that is premier among heterogeneous catalysts. The capacity for mild cation exchange in the material MFU-4l (MFU-4l = Zn[subscript 5]Cl[subscript 4](BTDD)[subscript 3], H[subscript 2]BTDD = bis(1H-1,2,3-triazolo[4,5-b],[4′,5′-i])dibenzo[1,4]dioxin) was leveraged 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 mol 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.