title: Mechanism of Molybdenum-Mediated Carbon Monoxide Deoxygenation and Coupling: Mono- and Dicarbyne Complexes Precede C-O Bond Cleavage and C-C Bond Formation.
abstract: Deoxygenative coupling of CO to value-added C≥2products is challenging and mechanistically poorly understood. Herein, we report a mechanistic investigation into the reductive coupling of CO, which provides new fundamental insights into a multielectron bond-breaking and bond-making transformation. In our studies, the formation of a bis(siloxycarbyne) complex precedes C-O bond cleavage. At -78 °C, over days, C-C coupling occurs without C-O cleavage. However, upon warming to 0 °C, C-O cleavage is observed from this bis(siloxycarbyne) complex. A siloxycarbyne/CO species undergoes C-O bond cleavage at lower temperatures, indicating that monosilylation, and a more electron-rich Mo center, favors deoxygenative pathways. From the bis(siloxycarbyne), isotopic labeling experiments and kinetics are consistent with a mechanism involving unimolecular silyl loss or C-O cleavage as rate-determining steps toward carbide formation. Reduction of Mo(IV) CO adducts of carbide and silylcarbyne species allowed for the spectroscopic detection of reduced silylcarbyne/CO and mixed silylcarbyne/siloxycarbyne complexes, respectively. Upon warming, both of these silylcarbynes undergo C-C bond formation, releasing silylated C2O1fragments and demonstrating that the multiple bonded terminal Mo≡C moiety is an intermediate on the path to deoxygenated, C-C coupled products. The electronic structures of Mo carbide and carbyne species were investigated quantum mechanically. Overall, the present studies establish the elementary reactions steps by which CO is cleaved and coupled at a single metal site.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard MC 127-72, Pasadena, California 91125, United States.
authors.forename: Joshua A
authors.initials: JA
authors.lastname: Buss
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard MC 127-72, Pasadena, California 91125, United States.
authors.forename: Theodor
authors.identifier: 0000-0002-9692-7614
authors.initials: T
authors.lastname: Agapie