LAUSR

The N-Heterocyclic Carbene (NHC) alane and gallane adducts (NHC)·Cp*AlH2 (NHC = Me2ImMe5, iPr2ImMe6, Dipp2Im 7) and (NHC)·Cp*GaH2 (NHC = Me2ImMe8, iPr2ImMe9, Dipp2Im 10; R2Im = 1,3-di-organyl-imidazolin-2-ylidene; Dipp = 2,6 diisopropylphenyl; Me2ImMe = 1,3,4,5-tetra-methyl-imidazolin-2-ylidene; Cp* = C5Me5) were prepared either via the reaction of (AlH2Cp*)31 with the NHC or by the treatment of (NHC)·GaH2I (NHC = Me2ImMe2, iPr2ImMe3, Dipp2Im 4) with KCp*. The reaction of (AlH2Cp*)31 with the backbone saturated NHC Dipp2ImH led to NHC ring expansion instead with the formation of (RER-Dipp2ImHH2)AlCp* 12. Heating solutions of the gallium compounds 8-10 triggered reductive elimination of Cp*H and afforded Cp*GaI16. The reaction of the alane adduct (Me2ImMe)·Cp*AlH25 with cAACMe led to the insertion of cAACMe into the Al-H bond with the formation of the compound rac-(Me2ImMe)·AlHCp*(cAACMeH) rac-14. Heating a solution of rac-14 led to irreversible isomerisation with the formation of (Me2ImMe)·AlHCp*(cAACMeH) meso-14. The alane adducts (iPr2ImMe)·Cp*AlH26 and (Dipp2Im)·Cp*AlH27 react with cAACMe with the release of the NHC and formation of the exceptionally stable oxidative addition product (cAACMeH)AlHCp* 15. Reactions of the gallane adducts 8-10 with cAACMe led to reductive elimination of cAACMe-H2 and the formation of Cp*GaI16.