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CO Reduction to CH3OSiMe3: Electrophile-Promoted Hydride Migration at a Single Fe Site.

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 (LnFe-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 LnFe-CH2OSiMe3 releases CH3OSiMe3, demonstrating net four-electron reduction of CO to CH3OSiMe3 at a single Fe site.

SUBMITTER: Deegan MM

PROVIDER: S-EPMC5509333 | biostudies-literature | 2017 Feb

REPOSITORIES: biostudies-literature

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CO Reduction to CH3OSiMe3: Electrophile-Promoted Hydride Migration at a Single Fe Site.

Deegan Meaghan M MM Peters Jonas C JC

Journal of the American Chemical Society 20170209 7

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 (LnFe-CH2</ ...[more]

PMID: 28156107

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