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首页> 外文期刊>Organometallics >Synthesis and Olefin Polymerization Catalysis of New Trivalent Samarium and Yttrium Complexes with Bridging Bis(cyclopentadienyl) Ligands
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Synthesis and Olefin Polymerization Catalysis of New Trivalent Samarium and Yttrium Complexes with Bridging Bis(cyclopentadienyl) Ligands

机译：桥联双（环戊二烯基）配体的新型三价Sa和钇配合物的合成和烯烃聚合催化

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摘要

New trivalent samarium and yttrium complexes with bridging bis(cyclopentadienyl) ligands were synthesized, and olefin polymerization catalysis of the complexes having an alkyl group [R = CH(SiMe_3)_2] on the metal was investigated. Three types of the rare earth halides (rac, C1, and mesa) whose structures differed with respect to the bridging group and the positions of substituents on the cyclopentadienyl (Cp) rings were prepared: rac-Sm-CI, Me_2Si[2,4- (Me3Si)2C_5H_2J2SmCI_2Li(THF)2 ( 1.a); C I-Sm -Cl, Me2Si [2,4-(Me_3Si)_2C_5H_2J [3,4.(Me_3Si)_2C5H_2J - SmCI_2Li(THF)_2 (2a); CJPh2Si)-Sm-CI, Ph2Si[2,4-(Me_3Si)_2C5H_2J[3,4.(Me3Si)2C~2]SmCI_2- Li(THF)2 (3); mesa-Sm-CI, [1,2-(Me_2Si)(Me2SiOSiMe_2)J(4-Me_3CC_5H_2)_2SmCI_2Li(THF)2 (4a); rac- Y -CI, Me_2Si[2,4-(Me3Si)2C5H212 YC12Li(THF)_2 (5a); C1- Y-CI, Me_2Si[2,4-(Me_3Si)_2C_5H_2] [3,4- (Me_3Si)_2C_5H_2]YCI_2Li(THF)_2 (6a); mesa. Y-CI, [1,2-(Me_2Si)(Me2SiOSiMe2)]( 4-Me3SiC5H_2)_2 YCl- (THF) (7a). Although the rac and C1 complexes (1.a, 2a and 5a, 6a) were obtained as an isomeric mixture by the reaction of LnCI3 {Ln = Sm, Y) with a dilithium salt of the ligand Me2Si[(Me3Si)2C5H3]2, it could be separated into both the pure complexes by utilizing the difference of solubility in hexanein each case. Structural data were obtained on la, 2a, 3, and 7a to confirm the structures expected from NMR spectroscopy. The (ring centroid)- metal-(ring centroid) angles in these complexes are ca. 10-20° smaller than those in nonbridging bis(cyclopentadienyl) rare earth complexes. The rare earth halides la, 2a, 4a, 5a, 6a, and 7areacted withLiCH(SiMe3h to afford rare earth alkyl complexes, rac-Sm-R, Me_2Si[2,4-(Me3Si)2C_5H_2]_2SmCH(SiMe_3)_2 {lb); C1-Sm-R, Me_2Si[2,4-(Me_3Si)_2C_5H_2][3,4-(Me3- Si)_2C_5H_2JSmCH(SiMe_3)_2 (2b); meso-Sm-R, [1,2-(Me2Si)(Me_2SiOSiMe_2)]( 4-Me_3CC_5H_2)_2SmCH - (SiMe_3)_2 {4b); rac-Y-R, Me_2Si[2,4.(Me3Si)_2C_5H_2]_2YCH(SiMe3)2 (5b); Cl"Y-R, Me_2Si[2,4- (Me3Si)2C5H2] [3,4-(Me_3Si)_2C_5H_2]YCH(SiMe_3)_2 (6b); meso-Y -R, and [1,2-(Me_2Si)(Me_2SiOSi- Me_2)](4-Me3SiC5H2)2YCH(SiMe_3)_2(7b), respectively. Only C1 type alkyl complexes (2b and 6b) polymerize ethylene, giving high molecular weight polyethylenes, and the precise structure of the active Sm complex 2b was determined by X-ray crystallography.
机译：合成具有桥联双（环戊二烯基）配体的新的三价sa和钇配合物，并研究了在金属上具有烷基[R = CH（SiMe_3）_2]的配合物的烯烃聚合催化作用。制备了三种类型的稀土卤化物（rac，C1和mesa），它们的结构与桥基和环戊二烯基（Cp）环上的取代基位置不同：rac-Sm-Cl，Me_2Si [2,4 -（Me3Si）2C_5H_2J2SmCl_2Li（THF）2（1.a）; C I-Sm -Cl，Me 2 Si [2,4-（Me_3Si）_2C_5H_2J [3,4。（Me_3Si）_2C5H_2J-SmCl_2Li（THF）_2（2a）; CJPh2Si）-Sm-Cl，Ph2Si [2,4-（Me_3Si）_2C5H_2J [3,4。（Me3Si）2C〜2] SmCl_2- Li（THF）2（3）; mesa-Sm-Cl，[1,2-（Me_2Si）（Me2SiOSiMe_2）J（4-Me_3CC_5H_2）_2SmCI_2Li（THF）2（4a）; rac-Y -Cl，Me_2Si [2,4-（Me3Si）2C5H212 YC12Li（THF）_2（5a）; C1-Y-Cl，Me_2Si [2,4-（Me_3Si）_2C_5H_2] [3,4-（Me_3Si）_2C_5H_2] YCI_2Li（THF）_2（6a）;台面。 Y-Cl，[1,2-（Me_2Si）（Me2SiOSiMe2）]（4-Me3SiC5H_2）_2 YCl-（THF）（7a）。尽管rac和C1配合物（1.a，2a和5a，6a）是通过LnCl3（Ln = Sm，Y）与配体Me2Si [（Me3Si）2C5H3] 2的二锂盐反应得到的异构体混合物，通过利用每种情况下在己烷中的溶解度差异，可以将其分为两种纯络合物。在1a，2a，3和7a上获得了结构数据，以确认NMR光谱预期的结构。这些络合物中的（环质心）-金属-（环质心）角为约。比非桥联双（环戊二烯基）稀土配合物小10-20°。稀土卤化物1a，2a，4a，5a，6a和7与LiCH（SiMe3h）反应得到稀土烷基络合物rac-Sm-R，Me_2Si [2,4-（Me3Si）2C_5H_2] _2SmCH（SiMe_3）_2 {lb ）; C1-Sm-R，Me_2Si [2,4-（Me_3Si）_2C_5H_2] [3,4-（Me3-Si）_2C_5H_2JSmCH（SiMe_3）_2（2b）; meso-Sm-R，[1,2-（Me2Si）（Me_2SiOSiMe_2）]（4-Me_3CC_5H_2）_2SmCH-（SiMe_3）_2 {4b）; rac-Y-R，Me_2Si [2,4。（Me3Si）_2C_5H_2] _2YCH（SiMe3）2（5b）; Cl“ YR，Me_2Si [2,4-（Me3Si）2C5H2] [3,4-（Me_3Si）_2C_5H_2] YCH（SiMe_3）_2（6b）; meso-Y -R和[1,2-（Me_2Si）（ Me_2SiOSi- Me_2）]（4-Me3SiC5H2）2YCH（SiMe_3）_2（7b）。只有C1型烷基络合物（2b和6b）聚合乙烯，得到高分子量的聚乙烯，以及活性Sm络合物2b的精确结构通过X射线晶体学测定。

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