title: Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst.
abstract: 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 = Zn5Cl4(BTDD)3, H2BTDD = 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.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Eric D
authors.initials: ED
authors.lastname: Metzger
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Carl K
authors.initials: CK
authors.lastname: Brozek
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Comito
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Mircea
authors.initials: M
authors.lastname: Dincă