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CO Reduction to CH_3OSiMe_3: Electrophile-Promoted Hydride Migration at a Single Fe Site

Deegan, Meaghan M. and Peters, Jonas C. (2017) CO Reduction to CH_3OSiMe_3: Electrophile-Promoted Hydride Migration at a Single Fe Site. Journal of the American Chemical Society, 139 (7). pp. 2561-2564. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170213-121746843

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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 H_2 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 (LnFe-CH_2OSiMe_3) 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 H_2 to LnFe-CH_2OSiMe_3 releases CH_3OSiMe_3, demonstrating net four-electron reduction of CO to CH_3OSiMe_3 at a single Fe site.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jacs.6b12444DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.6b12444PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.6b12444PublisherSupporting Information
ORCID:
AuthorORCID
Peters, Jonas C.0000-0002-6610-4414
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.
Funders:
Funding AgencyGrant Number
NIHGM070757
Gordon and Betty Moore FoundationUNSPECIFIED
Issue or Number:7
Record Number:CaltechAUTHORS:20170213-121746843
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170213-121746843
Official Citation:CO Reduction to CH3OSiMe3: Electrophile-Promoted Hydride Migration at a Single Fe Site Meaghan M. Deegan and Jonas C. Peters Journal of the American Chemical Society 2017 139 (7), 2561-2564 DOI: 10.1021/jacs.6b12444
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:74242
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:13 Feb 2017 21:02
Last Modified:03 Oct 2019 16:36

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