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Rare-Earth Metal Complexes Supported by Polydentate Phenoxy-Type Ligand Platforms: C-H Activation Reactivity and
Liye Qu1,2, Thierry Roisnel3, Marie Cordier3
1Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Dushu Lake Campus, Soochow University, Suzhou 215123, People's Republic of China.
Abstract:
Mono- and dinuclear group 3 metal complexes incorporating polydentate bis(imino)phenoxy {N2O}- and bis(amido)phenoxy {N2O}3- ligands were synthesized by alkane elimination reactions from the tris(alkyl) M(CH2SiMe3)3(THF)2 and M(CH2C6H4-o-NMe2)3 (M = Sc, Y) precursors. Complex 1a-Y was used for the selective C-H activation of 2-phenylpyridine at the 2'-phenyl position affording the corresponding bis(aryl) product 3a-Y, which was found to be reacted reluctantly with weak electrophiles (styrene, imines, hydrosilanes). The mechanism of formation of 3a-Y 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 CO2 promoted by 1a-Y (0.1-0.5 mol %) was demonstrated to proceed under mild conditions (toluene, 70 °C, PCO2 = 12 bar) giving polycarbonates with high efficiency (maximal TON of 460) and selectivity (97-99% of carbonate units).
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