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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis, characterization, and reactivity of dinuclear organo-rare-earth-metal alkyl complexes supported by 2-amidate-functionalized indolyl ligands: substituent effects on coordination and reactivity
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Synthesis, characterization, and reactivity of dinuclear organo-rare-earth-metal alkyl complexes supported by 2-amidate-functionalized indolyl ligands: substituent effects on coordination and reactivity

机译：由2-酰胺官能化吲哚基配体支持的二核有机稀土 - 稀土金属烷基复合物的合成，表征和反应性：对配位和反应性的取代基效应

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Two series of new dinuclear organo-rare-earth-metal alkyl complexes supported by 2-amidate-functionalized indolyl ligands with different haptic modes were synthesized and characterized. The treatment of [RE(CH2SiMe3)(3)(THF)(2)] with 1 equiv. of 2-(2,6-(Pr2C6H3NHC)-Pr-i?O)C8H5NH (H2L1) and 2-(2-(BuC6H4NHC)-Bu-t?O)C8H5NH (H2L2) in toluene yielded the dinuclear organo-rare-earth-metal alkyl complexes {[(1):((2)-(1):(1))-L-1]RE(CH2SiMe3)(THF)(2)}(2) [RE = Gd (1a), Dy (1b), Y (1c), Er (1d), and Yb (1e)] and {[(1):((2)-(1):(1)):(1)-L-2]RE(CH2SiMe3)(THF)(2)}(2) [RE = Gd (2a), Dy (2b), Y (2c), Er (2d), and Yb (2e)] in good yields. When [RE(CH2SiMe3)(3)(THF)(2)] were treated with 2 equiv. of H2L1 or H2L2 in THF, the dinuclear organo-rare-earth-metal complexes {((1):(1)-HL)[(1):((2)-(1):(1)):(1)-L]RE(THF)}(2) (1ca: RE = Y, L = L-1; 2ea: RE = Yb, L = L-2) were obtained. The complexes could react with small organic molecules such as N,N-diisopropylcarbodiimide (DIC), phenyl isocyanate, N-methylallylamine, phenylacetylene, pyridine, N-phenylimidazole, or 4-dimethylaminopyridine (DMAP) to yield a series of new complexes with different reactivity patterns along with the reported rare-earth-metal alkyl complexes. In the presence of cocatalysts, these dinuclear organo-rare-earth-metal alkyl complexes could initiate isoprene polymerization with high activity (100% conversion of 2000 equiv. of isoprene in 12 h), yielding polymers with high regioselectivity (1,4 polymers up to 96.1%).
机译：两个系列的通过2-酰胺化物官能化的吲哚基配体具有不同的触觉模式支持的新的双核有机稀土类金属络合物烷基合成和表征。的治疗[RE（CH2SiMe3）（3）（THF）（2）]与1个当量。的2-（2,6-（Pr2C6H3NHC）-Pr-I 2 O）C8H5NH（H2L1）和2-（2-（BuC6H4NHC）-Bu-T 2 O）C8H5NH（H2L2）的甲苯，得到双核有机稀有-earth金属烷基配合物{[（1）：（（2） - （1）:( 1）） - L-1] RE（CH2SiMe3）（THF）（2）} ...（2）[RE =钆（1A ），镝（1b）中，Y（1c）中，二（1D）和Yb（1E）]和{[（1）：（（2） - （1）:( 1））:( 1）-L- 2] RE（CH2SiMe3）以良好的收率（THF）（2）} ...（2）[RE =钆（2a）中，镝（2b）中，Y（2C），铒（2D）和Yb（2E）]。当[RE（CH2SiMe3）（3）（THF）（2）]用2当量处理。 H2L1或H2L2在THF中，双核有机稀土类金属络合物的{（（1）:( 1）-HL）[（1）：（（2） - （1）:( 1））:( 1 ）-L] RE（THF）}（2）（1CA：RE = Y，L = L-1; 2EA：镱，L =，得到L-2）RE =。复合物可以与诸如N，N-二异丙基（DIC），苯基异氰酸酯，N-甲基烯丙胺，苯乙炔，吡啶，N-苯基咪唑，或4-二甲基氨基吡啶（DMAP）的有机小分子反应产生一系列具有不同的新的复合物与已报道的稀土类金属络合物烷基沿着反应性模式。在助催化剂的存在下，这些双核有机稀土类金属络合物烷基可以发起以高活性聚合的异戊二烯（2000当量的100％的转化率在12小时异戊二烯。），得到的聚合物具有高的区域选择性（1,4聚合物向上96.1％）。

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    Hong Dongjing; Zhu Xiancui; Wang Shaowu; Wei Yun; Zhou Shuangliu; Huang Zeming; Zhu Shan; Wang Ruru; Yue Wenrun; Mu Xiaolong;

  • 作者单位

    Anhui Normal Univ Lab Funct Mol Solids Anhui Lab Mol Based Mat Minist Educ Coll Chem &

    Mat Sci Wuhu 241002 Anhui Peoples R China;

    Anhui Normal Univ Lab Funct Mol Solids Anhui Lab Mol Based Mat Minist Educ Coll Chem &

    Mat Sci Wuhu 241002 Anhui Peoples R China;

    Anhui Normal Univ Lab Funct Mol Solids Anhui Lab Mol Based Mat Minist Educ Coll Chem &

    Mat Sci Wuhu 241002 Anhui Peoples R China;

    Anhui Normal Univ Lab Funct Mol Solids Anhui Lab Mol Based Mat Minist Educ Coll Chem &

    Mat Sci Wuhu 241002 Anhui Peoples R China;

    Anhui Normal Univ Lab Funct Mol Solids Anhui Lab Mol Based Mat Minist Educ Coll Chem &

    Mat Sci Wuhu 241002 Anhui Peoples R China;

    Anhui Normal Univ Lab Funct Mol Solids Anhui Lab Mol Based Mat Minist Educ Coll Chem &

    Mat Sci Wuhu 241002 Anhui Peoples R China;

    Anhui Normal Univ Lab Funct Mol Solids Anhui Lab Mol Based Mat Minist Educ Coll Chem &

    Mat Sci Wuhu 241002 Anhui Peoples R China;

    Anhui Normal Univ Lab Funct Mol Solids Anhui Lab Mol Based Mat Minist Educ Coll Chem &

    Mat Sci Wuhu 241002 Anhui Peoples R China;

    Anhui Normal Univ Lab Funct Mol Solids Anhui Lab Mol Based Mat Minist Educ Coll Chem &

    Mat Sci Wuhu 241002 Anhui Peoples R China;

    Anhui Normal Univ Lab Funct Mol Solids Anhui Lab Mol Based Mat Minist Educ Coll Chem &

    Mat Sci Wuhu 241002 Anhui Peoples R China;

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  • 中图分类 化学;无机化学;
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