Rare-Earth Metal Complexes Supported by Polydentate Phenoxy-Type Ligand Platforms: C-H Activation Reactivity and CO(2)/Epoxide Copolymerization Catalysis - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2020

Rare-Earth Metal Complexes Supported by Polydentate Phenoxy-Type Ligand Platforms: C-H Activation Reactivity and CO(2)/Epoxide Copolymerization Catalysis

Résumé

Mono- and dinuclear group 3 metal complexes incorporating polydentate bis(imino)phenoxy {NO} and bis(amido)phenoxy {NO} ligands were synthesized by alkane elimination reactions from the tris(alkyl) M(CHSiMe)(THF) and M(CHCH--NMe) (M = Sc, Y) precursors. Complex was used for the selective C-H activation of 2-phenylpyridine at the 2'-phenyl position affording the corresponding bis(aryl) product , which was found to be reacted reluctantly with weak electrophiles (styrene, imines, hydrosilanes). The mechanism of formation of was established by DFT calculations, which also corroborated high stability of the complex toward insertion of styrene, apparently stemming from the inability to form the corresponding adduct. Copolymerization of cyclohexene oxide and CO promoted by (0.1-0.5 mol %) was demonstrated to proceed under mild conditions (toluene, 70 °C, = 12 bar) giving polycarbonates with high efficiency (maximal TON of 460) and selectivity (97-99% of carbonate units).

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Chimie
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Dates et versions

hal-03037791 , version 1 (14-12-2020)

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Liye Qu, Thierry Roisnel, Marie Cordier, Dan Yuan, Yingming Yao, et al.. Rare-Earth Metal Complexes Supported by Polydentate Phenoxy-Type Ligand Platforms: C-H Activation Reactivity and CO(2)/Epoxide Copolymerization Catalysis. Inorganic Chemistry, 2020, 59 (23), pp.16976-16987. ⟨10.1021/acs.inorgchem.0c02112⟩. ⟨hal-03037791⟩
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