Mechanism of Single-Site Molecule-Like Catalytic Ethylene Dimerization in Ni-MFU-4
Author(s)
Metzger, Eric Daniel
Comito, Robert J
Hendon, Christopher H
Dinca, Mircea
Date Issued
January 2017
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Metzger, Eric D. et al. “Mechanism of Single-Site Molecule-Like Catalytic Ethylene Dimerization in Ni-MFU-4l.” Journal of the American Chemical Society 139, 2 (January 2017): 757–762 © 2016 American Chemical Society
Version
Author's final manuscript
Abstract
A recently developed metal–organic framework (MOF) catalyst for the dimerization of ethylene has a combination of selectivity and activity that surpasses that of commercial homogeneous catalysts, which have dominated this important industrial process for nearly 50 years. The uniform catalytic sites available in MOFs provide a unique opportunity to directly study reaction mechanisms in heterogeneous catalysts, a problem typically intractable due to the multiplicity of coordination environments found in many solid catalysts. In this work, we use a combination of isotopic labeling studies, mechanistic probes, and DFT calculations to demonstrate 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. They provide a blueprint for the development of advanced heterogeneous catalysts with similar degrees of tunability to their homogeneous counterparts.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/jacs.6b10300
