[Y(η5:η1-C5Me4CH2SiMe2NCMe3)(CH2SiMe3)(THF)] | 380377-86-6

• 英文名称: [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(CH2SiMe3)(THF)]
• 英文别名: Y(η5-C5Me4CH2SiMe2NtBu-κN)(CH2SiMe3)(THF)
• CAS: 380377-86-6
• 化学式: C₂₄H₄₈NOSi₂Y
• 分子量: 511.728
• InChiKey: DVWZSKXTXFQJJD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(CH2SiMe3)(THF)] 、 2-甲基苯甲醚 以 苯 为溶剂， 以79%的产率得到[Y(η5:η1-C5Me4CH2SiMe2NCMe3)(CH2C6H4(OCH3)-2))(THF)]
  参考文献：
  名称：

  含连接的酰胺基-环戊二烯基配体的钇烷基络合物对芳族醚的邻位金属化

  摘要：

  半夹心的烷基配合物的反应[Y（η 5：η 1 -C 5我4 CH 2森达2 Ñ吨卜）（CH 2森达3）（THF）]（1）用苯甲醚顺利给出邻-金属化产物[Y（η 5：η 1 -C 5我4 CH 2森达2 ñ吨卜）（2-C 6 H ^ 4 OME）（THF）]（2）。3-和4-甲基苯甲醚以及苯酚类似地经历邻位-金属化，而硫代苯甲醚，N，N'-二甲基苯胺，氟苯和三氟苯不与钇配合物1反应。2-甲基茴香醚与发生反应1下的环甲基基团的活化，得到2-甲氧基苄基配合物[Y（η 5：η 1 -C 5我4 CH 2森达2 Ñ吨卜）（CH 2 ç 6 ħ 4 OMe- 2）（THF）]（6）。2-茴香基络合物2的单晶X射线结构分析揭示了四足的钢琴凳构型，其甲氧基与顺式配位于辅助配体的酰胺基官能团。

  DOI：

  10.1016/s0022-328x(03)00525-4
• 作为产物：
  描述：

  bis(tetrahydrofuran)tris(trimethylsilylmethyl)yttrium(III) 、 C₅(CH₃)4HCH₂Si(CH₃)2NHC(CH₃)3 以 正戊烷 为溶剂， 生成 [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(CH2SiMe3)(THF)]
  参考文献：
  名称：

  “Constrained geometry” catalysts of the rare-earth metals for the hydrosilylation of olefins

  摘要：

  A series of yttrium and lutetium alkyl complexes [Ln(eta(5)-C(5)Me(4)ZNR'-kappa N)(CH2SiMe3)(THF)(n)] (Ln = Y, Lu) was prepared by reacting the tris(trimethylsilylmethyl) precursor [Ln(CH2SiMe3)(3)(THF)(2)] with different linked amino-cyclopentadienes of the type (C5Me4H)ZNHR' (Z = SiMe2, CH2SiMe2; R'= tBu, Ph, C6H4-tBu-4, C6H4-nBu-4). The catalytic activity of these alkyl complexes in the hydrosilylation of 1-decene and styrene using PhSiH3 as reagent was examined under standard conditions. A significant influence of the ligand structure on the catalytic property (turnover frequency, regioselectivity) was observed with the yttrium. complex [Y(eta(5)-C(5)Me(4)CH(2)SiMe(2)NtBu-kappa N)(CH2SiMe3)(THF)] being the most active for 1-decene hydrosilylation. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.01.060
• 作为试剂：
  描述：

  正癸烯 、 苯硅烷 在 [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(CH2SiMe3)(THF)] 作用下， 以 氘代苯 为溶剂， 以100%的产率得到1-(phenylsilyl)decane
  参考文献：
  名称：

  “Constrained geometry” catalysts of the rare-earth metals for the hydrosilylation of olefins

  摘要：

  A series of yttrium and lutetium alkyl complexes [Ln(eta(5)-C(5)Me(4)ZNR'-kappa N)(CH2SiMe3)(THF)(n)] (Ln = Y, Lu) was prepared by reacting the tris(trimethylsilylmethyl) precursor [Ln(CH2SiMe3)(3)(THF)(2)] with different linked amino-cyclopentadienes of the type (C5Me4H)ZNHR' (Z = SiMe2, CH2SiMe2; R'= tBu, Ph, C6H4-tBu-4, C6H4-nBu-4). The catalytic activity of these alkyl complexes in the hydrosilylation of 1-decene and styrene using PhSiH3 as reagent was examined under standard conditions. A significant influence of the ligand structure on the catalytic property (turnover frequency, regioselectivity) was observed with the yttrium. complex [Y(eta(5)-C(5)Me(4)CH(2)SiMe(2)NtBu-kappa N)(CH2SiMe3)(THF)] being the most active for 1-decene hydrosilylation. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.01.060

文献信息

• Hydrosilylation of dienes by yttrium hydrido complexes containing a linked amido-cyclopentadienyl ligand
  作者：Alexander A. Trifonov、Thomas P. Spaniol、Jun Okuda

  DOI：10.1039/b406071g

  日期：——

  The dimeric hydrido complex [Y(L)(THF)(μ-H)]2 (2) containing the CH2SiMe2-linked amido-cyclopentadienyl ligand L = C5Me4CH2SiMe2NCMe32− catalyzed the hydrosilylation of 1,5-hexadiene, 1,7-octadiene and vinylcyclohexene by PhSiH3. As demonstrated for 1,7-octadiene, the product distribution of the hydrosilylation strongly depends on the molar ratio of the reagents. In the absence of PhSiH3, the stoichiometric reaction of 2 with 1,5-hexadiene gave the isolable crystalline cyclopentylmethyl complex [Y(L)CH2CH(CH2)4}(THF)] (3). Internal olefins such as trans-stilbene and alkynes such as tert-butylacetylene were not hydrosilylated by 2. trans-Stilbene was inserted into the yttrium–hydride bond of 2 to give the 1,2-diphenylethyl complex [Y(L)CH(CH2Ph)Ph}(THF)] (4). tert-Butylacetylene reacted with 2 to give the dimeric acetylide [Y(L)(CCCMe3)]2 (5). In an attempt to detect the monomeric hydrido species as a DME adduct [Y(L)H(DME)], complex 2 was reacted with DME to form the sparingly soluble, dimeric 2-methoxyethoxy complex [Y(L)(μ-OCH2CH2OMe-κO)]2 (6) under C–O splitting.

  二聚氢化物配合物 [Y(L)(THF)(μ-H)]₂ (2)，其中 L = C₅Me₄CH₂SiMe₂NCMe₃²⁻，催化了 1,5-己二烯、1,7-辛二烯和乙烯环己烯与 PhSiH₃ 的氢硅化反应。如对 1,7-辛二烯所示，氢硅化的产物分布强烈依赖于试剂的摩尔比。在没有 PhSiH₃ 的情况下，复合物 2 与 1,5-己二烯进行化学计量反应，给出了可分离的结晶环戊基甲基配合物 [Y(L)CH₂CH(CH₂)₄}(THF)] (3)。如顺式苯乙烯和叔丁炔等内部烯烃未被 2 氢硅化。顺式苯乙烯插入到 2 的钇-氢键中，生成了 1,2-二苯乙基配合物 [Y(L)CH(CH₂Ph)Ph}(THF)] (4)。叔丁炔与 2 反应生成二聚炔类 [Y(L)(CCCMe₃)]₂ (5)。为了探测作为 DME 加合物的单体氢化物物种 [Y(L)H(DME)]，复合物 2 与 DME 反应，形成了难溶性二聚 2-美氧乙氧基配合物 [Y(L)(μ-OCH₂CH₂OMe-κO)]₂ (6)，伴随 C–O 键断裂。
• Yttrium Hydrido Complexes that Contain a Less “Constrained Geometry” Ligand:  Synthesis, Structure, and Efficient Hydrosilylation Catalysis
  作者：Alexander A. Trifonov、Thomas P. Spaniol、Jun Okuda

  DOI：10.1021/om010518r

  日期：2001.11.1

  sigma -Bond metathesis of the new linked amino-cyclopentadiene (C5Me4H)CH2SiMe2NHCMe3 with Y(CH2SiMe3)(3)(THF)(2) gave the alkyl-yttrium complex [y(eta (5):eta (1)-C5Me4CH2SiMe2NCMe3)(CH2SiMe3)(THF)] (1) in 66% yield. Compound 1 was characterized by NMR spectroscopy and X-ray crystal structure analysis. By hydrogenolysis, 1 was quantitatively converted into the dimeric hydride [Y(eta (5):eta (1)-C5Me4CH2SiMe2NCMe3)(THF)(mu -H)](2) (2). X-ray crystal structure analysis revealed a Y2H2 core connected to two [Y(eta (5):eta (1)-C5Me4CH2SiMe2NCMe3)(THF)] fragments in a skewed manner, with a relatively long yttrium-yttrium distance of 3.7085(8) A. In solution, two diastereomers were observed by H-1 NMR spectroscopy at -78 degreesC. Dimer 2 was shown to efficiently catalyze the hydrosilylation of 1-decene with PhSiH3 to give the terminal silane (C10H21SiH2Ph)-C-n exclusively. Although the product of addition of the yttrium-hydride complex 2 to styrene, [Y(eta (5):eta (1)-C5Me4CH2SiMe2NCMe3)CH(CH3)Ph}(THF)] (3), contains a 1-phenethyl ligand derived from internal addition, hydrosilylation of styrene with PhSiH3 catalyzed by 2 gave both terminal- and internal-hydrosilylated products in a ratio of 1:1.4.