Homogeneous CO Hydrogenation: Dihydrogen Activation Involves a Frustrated Lewis Pair Instead of a Platinum Complex

During a search for conditions appropriate for Pt-catalyzed CO reduction using dihydrogen directly, metal-free conditions were discovered instead. A bulky, strong phosphazene base forms a "frustrated" Lewis pair (FLP) with a trialkylborane in the secondary coordination sphere of a rhenium carbonyl. Treatment of the FLP with dihydrogen cleanly affords multiple hydride transfers and C-C bond formation.