This work reports the cooperative reactivity of rare-earth aryloxide complexes with N-heterocyclic carbene (NHC) or N-heterocyclic olefin (NHO), showcasing their synergistic effect on the activation of H and diverse organic substrates. Reactions of RE(OAr) (RE=La, Sm, and Y; Ar=2,6-Bu-CH) with unsaturated NHC IBu (:C[N(R)CH], R=Bu) isolated abnormally bound RE metal NHC complexes RE/aNHC. In contrast, no metal-NHO adducts were formed when RE(OAr) were treated with NHO (RC=C[N(R)C(R)], R=CH). Both RE/aNHC and RE/NHO Lewis pairs enabled cooperative H activation. Furthermore, RE(OAr) were found to catalyze the hydrogenation of the exocyclic C=C double bond of NHO under mild conditions. Moreover, treatment of the La/aNHC complex with benzaldehyde produced a La/C4 1,2-addition product. The La/NHO Lewis pair could react with (trimethylsilyl)diazomethane and α, β-conjugated imine, affording an isocyanotrimethylsilyl lanthanum amide complex and a La/C 1,4-addition product, respectively.
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