[1,3-(SiMe3)2C3H3]^-₂Co | 832117-22-3

• 英文名称: [1,3-(SiMe3)2C3H3]^-₂Co
• CAS: 832117-22-3；850859-05-1
• 化学式: C₁₈H₄₂CoSi₄
• 分子量: 429.867
• InChiKey: OOYPBAOIPMVAPU-ORWWTJHYSA-N

计算性质

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

• 作为反应物：
  描述：

  [1,3-(SiMe3)2C3H3]^-₂Co 在 碘 作用下， 以 正己烷 为溶剂， 以76%的产率得到1,3,4,6-tetrakis(trimethylsilyl)-1,5-hexadiene
  参考文献：
  名称：

  平衡加合物的形成和与庞大的烯丙基配合物[1,3-（SiMe 3）2 C 3 H 3 ] 2 M（M = Fe，Co，Ni）的配体偶联

  摘要：

  在大气压下CO的通道通过A的解决方案' 2 M（M =铁，钴，镍; A'= [1,3-（森达3）2 C ^ 3 ħ 3 ] - ）在己烷中产生相应的烯丙基络合物甲' 2的Fe（CO）2，A'Co（CO）3，和A' 2分别的Ni（CO），。尽管铁和镍物质可以分离为纯净液体，但钴配合物伴随有偶联产物1,3,4,6-四（三甲基甲硅烷基）-1,5-己二烯。A'Co（CO）3由Co 2（CO）8，A'Br和PhCH 2 N（C2 H 5）3 + Cl –在含水碱中。所述IR拉伸A'的频率2的Fe（CO）2和A'Co（CO）3比在未取代的类似物低，表明trimethylsilated allyl配位体是一种较好的电子给体比亲本的版本。对配合物的各种构型进行密度泛函理论计算，再现了三甲基甲硅烷基的降频作用。他们还表明A'的形成，所述热力学2的Ni（CO）和未知（C 3 H ^ 5）2Ni（CO）相似，表

  DOI：

  10.1021/om5004573
• 作为产物：
  描述：

  cobalt(III) acetylacetonate 、 (1,3-bis(trimethylsilyl)allyl)potassium 以 乙醚 为溶剂， 以32.8%的产率得到[1,3-(SiMe3)2C3H3]^-₂Co
  参考文献：
  名称：

  与第4,5，9和10族金属甲硅烷基取代烯丙基化合物的反应：路线至η 3 -Allyls，亚烷基，和s ^ EC -烷基碳正离子

  摘要：

  甲硅烷基烯丙基E + [C 3 H 3（SiMe 3）2 -1,3] -（E = Li，K）的碱金属盐与第4组和第5组金属卤化物的反应生成了难处理的还原产物，的Co（ACAC）3和Ni（ACAC）2其中K反应[C 3 H ^ 3（森达3）2 -1,3]，得到共{η 3 -C 3 H ^ 3（森达3）2 -1,3} 2（1）和Ni {η 3 -C 3 H ^ 3（SiMe 3）2 -1,3} 2（2）。K [C 3 H 3（SiMe 3）2 -1,3]与Me 3 SnCl的反应得到Me 3 SiCH CHCH（SiMe 3）（SnMe 3）（3），后者与TaCl 5干净地反应得到{η 3 -C 3 H 3（SiMe 3）2 -1,3} TaCl 4（4）。用四甲基乙二胺处理该络合物导致HCl析出，烯丙基络合物转化为乙烯基亚烷基化合物Me 3 SiCH CHC（SiMe 3）TaCl 3（TMEDA）（5）。而在TACL的情况下5

  DOI：

  10.1021/om0491692

文献信息

• Chromium allyl and alkyl catalysts for the vinyl polymerization of norbornene and ethylene–norbornene copolymerizations
  作者：Timothy J. Woodman、Yann Sarazin、Shaun Garratt、Gerhard Fink、Manfred Bochmann

  DOI：10.1016/j.molcata.2005.03.017

  日期：2005.7

  Homoleptic allyl complexes of divalent metals. M-II[1.3-C3H3(SiMe3)(2)](2) (1, M=Cr: 2. M=Fe: 3, M=Ni 4, M=Co) activated with methylaluminoxane (MAO) have been tested as catalysts for the polymerization of norbortiene. Whereas the iron and cobalt systems were poorly active, both the nickel and chromium complexes were very productive and gave high molecular weight poly(norbornene)s. although the polymers generated by Cr and Ni differed significantly in the degree of stereoregularity. Cr-II[1,3-C3H3(SiMe3)(2)](2) polymerized ethylene in the absence of any cocatalyst but, surprisingly, was deactivated by MAO. whereas 1/B(C6F5)(3) showed moderate activity at 20 degrees C under 1 bar of ethylene. NMR experiments suggest that B(C6F5)(3) acts as a one-electron oxidant to generate the [Cr-III(allyl)(2)](+) cation, Although ethylene/norbornene copolymerizations were possible with 1/B(C6F5)(3), the activity was much lower than in ethylene homopolymerizations, and only limited amounts of norbornene could be incorporated. The catalytic behavior of this Cr(II) precursor contrasts sharply with that of the Cr(IV) alkyl complex Cr(CH2SiMe3)(4) (5)/MAO which polymerizes ethylene but reacts with norbornene to give oligomers. mostly trimers-pentamers. On the other hand, (5)/MAO is highly active for ethylene/norbornene copolymerizations and gives high molecular weight copolymers. Significantly, catalyst activity increases with increasing norbornene concentration. The copolymers show block-structure, and incorporated norbornene is present at the least as di-norbornene units, even at incorporation levels as low as 10 mol%. At higher norbornene concentrations, NNN sequences prevail. (c) 2005 Elsevier B.V. All rights reserved.
• Bis[1,3-bis(trimethylsilyl)allyl]cobalt(II), a stable electron-deficient allyl complex
  作者：J. Dominic Smith、Keith T. Quisenberry、Timothy P. Hanusa、William W. Brennessel

  DOI：10.1107/s0108270104020293

  日期：2004.10.15

  The title compound, bis[(1,2,3-eta)-(2E)-1,3-bis(trimethylsilyl)prop- 2-enyl] cobalt(II), [Co(C9H21Si2)(2)], is a homoleptic allyl complex with eta(3)-bound ligands. The Co - C distances range from 1.996 (3) to 2.096 (3) Angstrom and the allyl ligands adopt staggered, nearly parallel, arrangements around the Co atom. The trimethylsilyl groups are in syn - anti conformations; the steric shielding they provide to the metal is probably responsible for the thermal stability of the compound.