Homolysis of the Eu-N bond. Synthesis, structural characterization, and catalytic activity of novel europium(II) complexes
Homolysis of the Eu-N bond. Synthesis, structural characterization, and catalytic activity of novel europium(II) complexes
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DOI：
10.1021/om030306p
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发表时间：
2003-07
期刊：
影响因子：
2.8
通讯作者：
Shaowu Wang;Shuangliu Zhou;Enhong Sheng;M. Xie;Kehua Zhang;Lin Cheng;Yan-Ting Feng;Li Mao;Zixiang Huang
中科院分区：
文献类型：
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作者：
Shaowu Wang;Shuangliu Zhou;Enhong Sheng;M. Xie;Kehua Zhang;Lin Cheng;Yan-Ting Feng;Li Mao;Zixiang Huang
用C9H6RLi(R=H，Me)与ClCH2SiMe2Cl2反应，然后用吡咯烷化锂C4H8NLi反应，合成了两个新的吲哚化合物C9H7CH2SiMe2NC4H8(1)和C9H6-1-Me-3-CH2SiMe2NC4H8(2)。在回流甲苯中，[(Me_3Si)_2N]_3Eu(μ-Cl)Li(Thf)_3与2当量的1反应，通过串联硅胺消除、Eu~(3+)还原为Eu~(2+)、C-−-C偶联反应，合成了一种新型的三层夹心四核Eu(II)化合物Eu(3)。为了探索配合物3的形成途径，研究了C9H6-1-Me-3-CH2SiMe2NC4H8(3)与[(Me_3Si)_2N]_3Eu(μ-Cl)Li(THF)_3的相互作用。[(Me_3Si)_2N]_3Eu(μ-Cl)Li(Thf)_3与2当量2在回流甲苯温度或60℃反应后，通过串联硅胺消除/均解制得单体Eu(II)配合物(η_5：η_1-C_9H_5-1-Me-3-CH_2SiMe_2NC4H_8)_2Eu(4).
Two new indene compounds, C9H7CH2SiMe2NC4H8 (1) and C9H6-1-Me-3-CH2SiMe2NC4H8 (2), were synthesized by the reaction of C9H6RLi (R = H, Me) with ClCH2SiMe2Cl, followed by treatment with lithium pyrrolidinide C4H8NLi. The interaction of [(Me3Si)2N]3Eu(μ-Cl)Li(THF)3 with 2 equiv of 1 in refluxing toluene produced, after workup, a novel triple-decker sandwich tetranuclear europium(II) compound, [{η:5η:5η1-(C9H5CH2SiMe2NC4H8)2}Eu2(μ-Cl)]2[μ-η3:η5:η1:η3:η5:η1-(C9H5CH2SiMe2NC4H8)2]·C7H8·(C6H6)0.5 (3), with a coupled indenyl ligand through tandem silylamine elimination, reduction of Eu3+ to Eu2+, and the C−C coupling reactions. To probe the formation pathway of complex 3, the interaction of C9H6-1-Me-3-CH2SiMe2NC4H8 (3) with [(Me3Si)2N]3Eu(μ-Cl)Li(THF)3 was studied. Treatment of [(Me3Si)2N]3Eu(μ-Cl)Li(THF)3 with 2 equiv of 2 in refluxing toluene temperature or at 60 °C produced, after workup, a monomeric europium(II) complex, (η5:η1-C9H5-1-Me-3-CH2SiMe2NC4H8)2Eu (4), via tandem silylamine elimination/homolysis of...