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Synthesis, characterization and catalytic activity of rare-earth metal amides incorporating cyclohexyl bridged bis(β-diketiminato) ligands

机译:含环己基桥联的双(β-二酮亚胺基)配体的稀土金属酰胺的合成,表征和催化活性

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A series of organo rare-earth metal amides incorporating chiral cyclohexyl bridged bis(β-diketiminato) ligands with general formula LREN(SiMe3)2 (L1 = (1S,2S)-1,2-Cy[NC(Me)CHC(Me)NAr]2, Ar = 2, 6-Et2C6H3, RE = Nd (1a), Dy (1b), Yb (1c), Y (1d); L2 = (1R,2R)-1,2-Cy[NC(Me)CHC(Me)NAr]2, Ar = 2, 6-i-Pr2C6H3, RE = Nd (2a), Gd (2b), Dy (2c), Er (2d), Y (2e)) were synthesized in good yields via reactions of [(Me3Si)2N]3REIII(μ-Cl)Li(THF)3 with H2L1 and H2L2. All compounds were fully characterized by spectroscopic methods and elemental analyses. The complexes 1d and 2e were also characterized by 1H NMR and 13C NMR spectral analyses. The structures of complexes 1a–d were determined by single-crystal X-ray analyses. Investigation of the catalytic properties of the complexes indicated that all complexes exhibited a high catalytic activity towards the addition of diphenylphosphine oxide to β-nitroalkene and α,β-unsaturated carbonyl derivatives with an excellent regioselectivity.
机译:一系列手性环己基桥联的双(β-二酮亚胺基)配体的有机稀土金属酰胺,通式为LREN(SiMe 3 2 < / sub> (L 1 =(1 S ,2 S )-1,2 -Cy [NC(Me)CHC(Me)NAr] 2 ,Ar = 2,6-Et 2 C 6 H 3 ,RE = Nd(1a),Dy(1b),Yb(1c) ,Y(1d); L 2 =(1 R ,2 R )-1,2-Cy [NC(Me)CHC(Me)NAr] 2 ,Ar = 2、6- i -Pr 2 C 6 H 3 ,RE = Nd(2a),Gd( 2b),Dy(2c),Er(2d),Y(2e))通过[(Me 3 > Si) 2 N] 3 RE III (μ-Cl)Li(THF) 3 和H 2 L 1 和H < small> 2 L 2 。所有化合物均通过光谱法和元素分析得到了充分表征。配合物1d和2e还通过 1 H NMR和 13 C NMR光谱进行表征。配合物1a-d的结构通过单晶X射线分析确定。对配合物的催化性能的研究表明,所有配合物均表现出对将二苯基膦氧化物加至β-硝基烯烃和α,β-不饱和羰基衍生物具有很高的区域选择性的高催化活性。

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