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

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.