Highly Selective Olefin Trimerization Catalysis by a Borane-Activated Titanium Trimethyl Complex
Abstract
Reaction of a trimethyl titanium complex, (FI)TiMe_3 (FI = phenoxy-imine), with 1 equiv of B(C_6F_5)_3 gives [(FI)TiMe_2][MeB(C_6F_5)_3], an effective precatalyst for the selective trimerization of ethylene. Mechanistic studies indicate that catalyst initiation involves generation of an active TiII species by olefin insertion into a Ti–Me bond, followed by β-H elimination and reductive elimination of methane, and that initiation is slow relative to trimerization. (FI)TiMe_3/B(C_6F_5)_3 also leads to a competent catalyst for the oligomerization of α-olefins, displaying high selectivity for trimers (>95%), approximately 85% of which are one regioisomer. This catalyst system thus shows promise for selectively converting light α-olefins into transportation fuels and lubricants.
Additional Information
© 2013 American Chemical Society. Received: November 12, 2013; Published: November 27, 2013. We thank David VanderVelde for help setting up several NMR experiments, Larry Henling for assistance with crystallographic work, Angelo Di Bilio, Loi Do, and John Anderson for help with EPR experiments, and Harry B. Gray and Jay R. Winkler for helpful discussions. This work was funded by BP through the XC2 program.Attached Files
Supplemental Material - om401098m_si_001.pdf
Supplemental Material - om401098m_si_002.cif
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Additional details
- Eprint ID
- 42809
- Resolver ID
- CaltechAUTHORS:20131203-152859954
- BP XC2 Program
- Created
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2013-12-03Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field