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
