[(η⁵--C₅HMe₄)₂Zr(η²-bis(trimethylsilyl)acetylene)] | 180400-35-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: [(η⁵--C₅HMe₄)₂Zr(η²-bis(trimethylsilyl)acetylene)]
• 英文别名: [(η⁵--C₅HMe₄)₂Zr(η²-BTMSA)]；bis(η5-tetramethylcyclopentadienyl)(η2-bis(trimethylsilyl)ethyne)zirconium(IV)；(C5HMe4)2Zr(η(2)-C2(SiMe3)2)；1,2,3,5-tetramethylcyclopenta-1,3-diene;trimethyl(2-trimethylsilylethynyl)silane;zirconium(2+)
• CAS: 180400-35-5
• 化学式: C₂₆H₄₄Si₂Zr
• 分子量: 504.03
• InChiKey: YDFBYKVISAVNKL-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：
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• 环数：
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• 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：

  3,3-二甲基-1-丁炔 、 [(η⁵--C₅HMe₄)₂Zr(η²-bis(trimethylsilyl)acetylene)] 以 正己烷 为溶剂， 以95%的产率得到bis(η5-tetramethylcyclopentadienyl)(η1-tert-butylethynyl)(η3-1,2-bis(trimethylsilyl)ethenyl)zirconium(IV)
  参考文献：
  名称：

  Reactions of Substituted Zirconocene−Bis(trimethylsilyl)ethyne Complexes with Terminal Alkynes

  摘要：

  The complexes [Zr(eta(2)-Me(3)SiCequivalent toCSiMe(3))(eta(5)-C5Me4R)(2)] (R = Me (5), H (6), SiMe3 (7)) reacted smoothly with terminal alkynes HCequivalent toCR' (R' = CMe3, SiMe3, ferrocenyl (Fc), Ph) to give the agostic alkenyl-alkynyl complexes [Zr(eta(1)-Cequivalent toCR'){eta(3)-C(SiMe3)=CH(SiMe3)}(eta(5)-C5Me4R)(2)] (R/ R'= Me/CMe3 (5a), Me/SiMe3 (5b), H/CMe3 (6a), H/SiMe3 (6b), H/Fc (6c), H/Ph (6d), SiMe3/ CMe3 (7a), SiMe3/Fc (7c)). Complex 7a, formed in situ from 7 and HCequivalent toCCMe(3), dimerized tert-butylethyne exclusively to give the head-to-tail dimer Me(3)CCequivalent toCC(CMe3)=CH2, and when all the terminal alkyne was consumed, 7 was restored. Complex 7 reacted similarly with 1-hexyne, phenylethyne, and (trimethylsilyl)ethyne, affording the respective alkenyl-alkynyl complexes, which also changed back to 7 on evaporation of the reaction solutions; none of these terminal alkynes was dimerized with 5-7. Heating of complex 6 with LiCequivalent toCSiMe(3) in toluene or THF yielded the diamagnetic zirconate complex Li[Zr(eta(1)-Cequivalent toCSiMe(3))(eta(2)-Me(3)SiCequivalent toCSiMe(3))(eta(5)-C5HMe4)(2)] (6e) and its solvatomorph Li[Zr(eta(1)-Cequivalent toCSiMe(3))(eta(2)-Me(3)SiCequivalent toCSiMe(3))( C5HMe4)(2)] . C4H8O (6f), respectively. The lithium cation in 6e and 6f is placed in a position at the side of the alkynyl triple bond and close to C-beta of the eta(2)-Me(3)SiCequivalent toCSiMe(3) ligand, apparently interacting with both moieties. All presented complexes were characterized by the standard spectral methods, and the structures of 5a, 6a, 6c, 6d, and 6e were determined by single-crystal X-ray diffraction.

  DOI：

  10.1021/om040042m
• 作为产物：
  描述：

  [(η⁵-C₅HMe₄)₂ZrH{C(SiMe₃)-CH(SiMe₃)}] 以 氘代甲苯 为溶剂， 生成 [(η⁵--C₅HMe₄)₂Zr(η²-bis(trimethylsilyl)acetylene)]
  参考文献：
  名称：

  钛茂和锆茂双（三甲基甲硅烷基）乙炔配合物的氢化†

  摘要：

  下最大大气压加入二氢双（三甲基甲硅烷基）乙炔（BTMSA）二茂钛络合物，[（η以下反应5 -C 5 ħ 5- Ñ我Ñ）2的Ti（η 2 -BTMSA）]（Ñ = 0 ，1，3和4）（图1A-1D），和二茂锆，[（η 5 -C 5 H ^ 5- ñ我ñ）2锆（η 2 -BTMSA）]（ñ = 2-5）（4A- 4D），以不同的方式进行，并根据金属的不同提供了不同的产品。在所有情况下，前者的配合物在80°C下反应延长时，都会通过氢化成双1,2-（三甲基甲硅烷基）乙烷而失去其BTMSA配体。对于Ñ = 0,1，和3，所形成的二茂钛物种原位二聚经由富瓦烯配体和两个桥接配体氢化物的形成，使公知的绿色二聚体二茂钛（2A-2C）。对于Ñ = 4，二茂钛氢化物[（η 5 -C 5 HME 4）2 TIH]（2D）中的溶液形成的，类似于已知的[（η 5-C 5 Me 5）2 TiH]（2E），n = 5；然

  DOI：

  10.1039/c8dt01909f

文献信息

• Methyl-Substituted Zirconocene−Bis(trimethylsilyl)acetylene Complexes (C₅H₅_-<i>_n</i>Me<i>_n</i>)₂Zr(η²-Me₃SiC⋮CSiMe₃) (<i>n</i> = 2−5)
  作者：Jörg Hiller、Ulf Thewalt、Miroslav Polášek、Lidmila Petrusová、Vojtech Varga、Petr Sedmera、Karel Mach

  DOI：10.1021/om960184j

  日期：1996.8.20

  The (C(5)H(5-n)Me(n))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (n = 2-5; 1,3-dimethyl, 1,2,3-trimethyl) (2C-F) complexes were prepared by the reduction of corresponding zirconocene dichlorides with magnesium in THF in the presence of bis(trimethylsilyl)acetylene (BTMSA). All of them are stable in the absence of THF. Crystal structures of (C(5)HMe(4))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (2E) and (C(5)Me(5))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (2F) and ofthe analogous titanium complexes are isomorphous. The red shift of the nu(C=C) vibration and the downfield shift of C-13 delta(C=C) indicate that BTMSA in 2C-F is more strongly coordinated than in analogous titanocene complexes. The nonisolated complex (C(5)H(4)Me)(2)Zr[eta(2)-C-2(SiMe(3))(2)](THF) (2B . THF) rearranges after the loss of THF to give the dimer [(eta(5)-C(5)H(4)Me)(eta(1)-C(SiMe(3))=CH(SiMe(3))Zr(mu-eta(1):eta(5)-C(5)H(3)Me)](2) (3B).