Journal of the American Chemical Society
Article
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complexes, by replacing the 2-isopropoxy substituent in
complexes 1 and 2 by a smaller 2-methoxy group in
complexes 3, leads to a pronounced acceleration of the
olefin-dependent Ia mechanism and consequently to a
strong increase in the rate of precatalyst activation at high
olefin concentrations.
(iii) Electron-rich and sterically less demanding olefins, such
as 1-hexene or BuVE, prefer the Ia activation. For the
more bulky or less electron-rich olefins, such as DEDAM
and styrene, the dissociative pathway is more important
with bulky complexes 1 and 2. With the less bulky
complexes 3, the olefin DEDAM undergoes precatalyst
activation preferentially according to Ia, while styrene is a
borderline case with comparable D and Ia contributions.
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In order to achieve rapid precatalyst initiation an electron-
deficient and sterically accessible ruthenium is ideal, while the
olefins should be electron-rich and sterically unhindered to
promote both the dissociative as well as the interchange
activation pathway. The combination of steric and electronic
effects leads to Grubbs−Hoveyda-type complexes with widely
differing rates of precatalyst activation. Complex 3(NO2) with
4-NO2 and 2-methoxy substituents initiates ca. 1000 times
faster with DEDAM than precatalyst 1(NEt2) with 4-NEt2 and
2-isopropoxy substituents.
It remains to be shown in the future whether such a toolbox
of catalysts with tunable initiation rates can be used for more
efficient olefin metathesis transformations, by using precatalysts
whose initiation rate is tailored to the needs of a specific
substrate. Accepting the dual mechanism for precatalyst
activation also helps to understand why different combinations
of precatalysts and substrate lead to widely different reactivities
in olefin metathesis reactions, despite the fact that the same
catalytically active species is formed.
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ASSOCIATED CONTENT
* Supporting Information
Experimental procedures for the synthesis of ligands and
ruthenium complexes and characterization of complexes, copies
of NMR and mass spectra, formal kinetics, Eyring plots, and
cyclic voltammograms. This material is available free of charge
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AUTHOR INFORMATION
Corresponding Author
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ACKNOWLEDGMENTS
■
We thank the DFG for support through grant Pl 178/8-3. We
are grateful to Dr. X. Solans-Montfort for useful discussions and
the Umicore AG for a donation of M31 complex.
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