Journal of the American Chemical Society
Article
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CONCLUSIONS
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A comprehensive kinetic study of five catalytic systems based
on Zr amine bis-phenolate complexes has been completed, and
the relevant rate constants and elementary reaction steps were
robustly determined for each system. The mechanism includes
initiation, normal propagation, misinsertion, recovery, and
chain transfer. The most significant finding was an apparent
correlation between the zirconium pendant ligand (Zr−X)
bond distance and the rate constants of chain transfer.
Specifically, for catalysts 1−3, the logarithm of the chain
transfer rate constants (kvinylidene and kvinylene) increase linearly
with the Zr−X bond distance. Once a certain Zr−X bond
distance is reached, the chain transfer mechanism changes from
monomer independent β-H elimination to monomer depend-
ent β-H transfer (to monomer), as observed for systems 4 and
5. This study has also shown that, with the exception of 4, the
rate of misinsertion (kmis) increases for a longer Zr−X bond
distance, which is most likely due to an increase in the steric
freedom allowing for an increase in misinsertion events, regio
errors.
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ASSOCIATED CONTENT
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S
* Supporting Information
Synthesis of all ligands and precatalysts, as well as a complete
set of experimental procedures for each system and kinetic
modeling. This material is available free of charge via the
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AUTHOR INFORMATION
references therein.
■
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Corresponding Author
Author Contributions
All authors have given approval to the final version of the
manuscript.
Notes
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The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support was provided by the U.S. Department of
Energy by Grant No. DE-FG02-03ER15466. This research was
supported in part by the National Science Foundation through
TeraGrid resources provided by Purdue University under grant
number TG-CTS070034N. Computing resources were also
provided by Information Technology at Purdue.
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