Reductive‐Transmetalation Reactions of ZnR2/(AlCp*)4 Heterobimetallic Combinations and Application towards CO2 Insertion

Organo‐aluminum compounds are usually derived via salt metathesis reactions starting from aluminum halides and s‐block organometallics such as organolithiums or Grignard reagents. Herein, an alternative route is reported using an Cp*Al(I)/Zn(II)R 2 (Cp* = C 5 Me 5 ; R = aryl) system which facilitates the formation of a range of halide and donor free heteroleptic triorgano‐alanes of the general formula [Al(Cp*)R 2 ]. Exposing the obtained alanes to an atmosphere of CO 2 enables for the selective insertion of CO 2 in their AlCp* moieties. State of the art quantum chemical calculations support experimental observations providing mechanistic insights on the observed reactivity of the [Al(Cp*)R 2 ] compounds towards this unsaturated organic molecule.