Mechanism of Single-Site Molecule-Like Catalytic Ethylene Dimerization in Ni-MFU-4l
| Autor: | Christopher H. Hendon, Mircea Dincă, Robert J. Comito, Eric D. Metzger |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
Reaction mechanism
Ethylene 010405 organic chemistry General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Combinatorial chemistry Catalysis 0104 chemical sciences Isotopic labeling Metal chemistry.chemical_compound Colloid and Surface Chemistry chemistry Transition metal visual_art visual_art.visual_art_medium Molecule Organic chemistry Selectivity |
| Zdroj: | Journal of the American Chemical Society. 139(2) |
| ISSN: | 1520-5126 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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