Frustrated Al/M Heterobimetallic Complexes (M = Cr, Mo, W) That Exhibit Both Lewis and Radical Pair Behavior

Exploration of new heterobinuclear Al/M combinations is relevant to contemporary strategies for cooperative bond activation. Here, we report the synthesis and characterization of six new Al/M heterobimetallic complexes (M = Cr, Mo, W) that exhibit end-on "isocarbonyl"-type Al─O═C═M bridges with metalloketene character rather than featuring Al─M─C≡O motifs with metal-metal bonding. The new compounds were characterized experimentally by nuclear magnetic resonance and infrared spectroscopies and theoretically using density functional theory, natural bond orbital, and quantum theory of atoms in molecules calculations. Factors influencing Al─O═C═M vs Al─M─C≡O isomerism were probed both experimentally and computationally. Crossover experiments between different group VI Al/M derivatives and regioselective epoxide ring opening indicate that the Al/M complexes act as masked frustrated Lewis pairs in solution under certain conditions. However, crossover experiments between group VI Al/M complexes and a previously studied Al-Fe complex, as well as computational modeling, imply that the same complexes can also reasonably act as masked frustrated radical pairs (FRPs). FRP reactivity with the group VI Al/M complexes was achieved under photochemical conditions, producing unsaturated metal-carbonyl dimers [(CpCr)₂(CO)₃]^2- and [Mn₂(CO)₈]^2-, which would otherwise be unstable under standard conditions but that are isolable here due to Al(III) coordination. The metal-metal bonding in these unsaturated metal-carbonyl dimers was also analyzed theoretically.