ja6b10300_si_002.xlsx (113.65 kB)
Mechanism of Single-Site Molecule-Like Catalytic Ethylene Dimerization in Ni-MFU‑4l
dataset
posted on 2016-12-14, 00:00 authored by Eric D. Metzger, Robert J. Comito, Christopher H. Hendon, Mircea DincăA 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.