chromium(2+);trimethyl-[(E)-3-trimethylsilylprop-1-enyl]silane | 885316-09-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: chromium(2+);trimethyl-[(E)-3-trimethylsilylprop-1-enyl]silane
• CAS: 885316-09-6
• 化学式: C₁₈H₄₂CrSi₄
• 分子量: 422.869
• InChiKey: JUPLVHKLKJREPT-ORWWTJHYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  AgI*P(CH3)3 、 chromium(2+);trimethyl-[(E)-3-trimethylsilylprop-1-enyl]silane 以 正己烷 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  铬与三甲基甲硅烷基化配体的均质烯丙基配合物。{[1-（SiMe 3）C 3 H 4 ] 2 Cr} 2，[1,3-（SiMe 3）2 C 3 H 3 ] 2 Cr和[1,1'，3- （SiMe 3）3 C 3 H 2 ] 2 Cr

  摘要：

  两当量的K [1-（SiMe 3）C 3 H 4 ]，K [1,3-（SiMe 3）2 C 3 H 3 ]或K [1,1'，3-（SiMe 3）反应3 C 3 H 2 ]和CrCl 2在-78°C下的THF中生成红色络合物{[1-（SiMe 3）C 3 H 4 ] 2 Cr} 2（1），[1,3-（SiMe 3）2 C 3 H 3 ] 2 Cr（2）和[1,1'，3-（SiMe3）3 C 3 H 2 ] 2 Cr（3）。它们是热稳定的化合物，对于单体2和3来说非常明显，它们具有正式的12电子计数。单晶X射线结构证实了{[1-（SiMe 3）C 3 H 4 ] 2 Cr} 2的二聚性质，它是围绕CrCr'= 1.9784（7）的Cr 2核构造的。在单体络合物中，烯丙基配体以三全能方式与金属键合，CrC距离为2.193（2）–2.257（2）Åin 2和2.223（5）–2.319（5）Åin

  DOI：

  10.1016/s0022-328x(03)00603-x
• 作为产物：
  描述：

  chromium dichloride 、 (1,3-bis(trimethylsilyl)allyl)potassium 以 四氢呋喃 为溶剂， 以74.9%的产率得到chromium(2+);trimethyl-[(E)-3-trimethylsilylprop-1-enyl]silane
  参考文献：
  名称：

  Chromium allyl and alkyl catalysts for the vinyl polymerization of norbornene and ethylene–norbornene copolymerizations

  摘要：

  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.

  DOI：

  10.1016/j.molcata.2005.03.017

文献信息

• Steric Stabilization of Homoleptic Bis(π-allyl) Complexes of Chromium(II) and Iron(II)
  作者：J. Dominic Smith、Timothy P. Hanusa、Victor G. Young

  DOI：10.1021/ja015626j

  日期：2001.7.1