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 H2and 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 H2to LnFe-CH2OSiMe3releases CH3OSiMe3, demonstrating net four-electron reduction of CO to CH3OSiMe3at a single Fe site.
Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
Meaghan M
MM
Deegan
Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
Jonas C
0000-0002-6610-4414
JC
Peters
D001665:Binding Sites; D002248:Carbon Monoxide / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D012825:Silicon / Q000737:chemistry*
D056831:Coordination Complexes; D002248:Carbon Monoxide; D006859:Hydrogen; D007501:Iron; D012825:Silicon