CO Reduction to CH₃OSiMe₃: Electrophile-Promoted Hydride Migration at a Single Fe Site
- Creators
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Deegan, Meaghan M.
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Peters, Jonas C.
Abstract
One of the major challenges associated with developing molecular Fischer–Tropsch catalysts is the design of systems that promote the formation of C–H bonds from H₂ and CO while also facilitating the release of the resulting CO-derived organic products. To this end, we describe the synthesis of reduced iron-hydride/carbonyl complexes that enable an electrophile-promoted hydride migration process, resulting in the reduction of coordinated CO to a siloxymethyl (L_nFe-CH₂OSiMe₃) group. Intramolecular hydride-to-CO migrations are extremely rare, and to our knowledge the system described herein is the first example where such a process can be accessed from a thermally stable M(CO)(H) complex. Further addition of H₂ to L_nFe-CH₂OSiMe₃ releases CH_₃OSiMe₃, demonstrating net four-electron reduction of CO to CH₃OSiMe₃ at a single Fe site.
Additional Information
© 2017 American Chemical Society. Received: December 2, 2016; Published: February 3, 2017. This work was supported by the NIH (GM070757) and the Gordon and Betty Moore Foundation. We thank Larry Henling and Mike Takase for assistance with crystallography. The authors declare no competing financial interest.Attached Files
Accepted Version - nihms877881.pdf
Supplemental Material - ja6b12444_si_001.pdf
Supplemental Material - ja6b12444_si_002.cif
Files
Additional details
- PMCID
- PMC5509333
- Eprint ID
- 74242
- Resolver ID
- CaltechAUTHORS:20170213-121746843
- NIH
- GM070757
- Gordon and Betty Moore Foundation
- Created
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2017-02-13Created from EPrint's datestamp field
- Updated
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2022-04-05Created from EPrint's last_modified field