Coordination and Homologation of CO at Al(I): Mechanism and Chain Growth, Branching, Isomerization, and Reduction

Homologation of carbon monoxide is central to the heterogeneous Fischer-Tropsch process for the production of hydrocarbon fuels. C-C bond formation has been modeled by homogeneous systems, with [C n O n ] 2- fragments ( n = 2-6) formed by two-electron reduction being commonly encountered. Here, we show that four- or six-electron reduction of CO can be accomplished by the use of anionic aluminum(I) ("aluminyl") compounds to give both topologically linear and branched C 4 /C 6 chains. We show that the mechanism for homologation relies on the highly electron-rich nature of the aluminyl reagent and on an unusual mode of interaction of the CO molecule, which behaves primarily as a Z-type ligand in initial adduct formation. The formation of [C 6 O 6 ] 4- from [C 4 O 4 ] 4- shows for the first time a solution-phase CO homologation process that brings about chain branching via complete C-O bond cleavage, while a comparison of the linear [C 4 O 4 ] 4- system with the [C 4 O 4 ] 6- congener formed under more reducing conditions models the net conversion of C-O bonds to C-C bonds in the presence of additional reductants.