Frustrated Lewis Pair-Type Reactivity of Intermolecular Rare-Earth Aryloxide and N-Heterocyclic Carbene/Olefin Combinations

Chem Asian J. 2024 Mar 7:e202400190. doi: 10.1002/asia.202400190. Online ahead of print.ABSTRACTThis work reports the cooperative reactivity of rare-earth aryloxide complexes with N-heterocyclic carbene (NHC) or N-heterocyclic olefin (NHO), showcasing their synergistic effect in the activation of H2 and diverse organic substrates. Reactions of RE(OAr)3 (RE = La, Sm, and Y; Ar = 2,6-tBu2-C6H3) with unsaturated NHC ItBu (:C[N(R)CH]2, R = tBu) isolate abnormally bound RE metal NHC complexes RE/aNHC. In contrast, no metal-NHO adducts were formed when RE(OAr)3 were treated with NHO (R2C=C[N(R)C(R)]2, R = CH3). Both RE/aNHC and RE/NHO Lewis pairs enabled cooperative H2 activation. Furthermore, RE(OAr)3 were found to catalyze the hydrogenation of 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 a, b-conjugated imine, affording an isocyanotrimethylsilyl lanthanum amide complex and a La/C 1,4-addition product, respectively.PMID:38451014 | DOI:10.1002/asia.202400190

Source: Chemistry, an Asian Journal - March 7, 2024 Category: Chemistry Authors: Yiwen Guan Kejian Chang Yujie Su Xian Xu Xin Xu Source Type: research