[1,3-(SiMe₃)₂C₃H₃]^-₂Ni | 850859-06-2

• 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: [1,3-(SiMe₃)₂C₃H₃]^-₂Ni
• 英文别名: nickel(2+);trimethyl-[(E)-3-trimethylsilylprop-1-enyl]silane
• CAS: 850859-06-2
• 化学式: C₁₈H₄₂NiSi₄
• 分子量: 429.563
• InChiKey: FKTNJHKDUZZBGT-ORWWTJHYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.0
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [1,3-(SiMe₃)₂C₃H₃]^-₂Ni 、 一氧化碳 以 正己烷 为溶剂， -78.0 ℃ 、101.33 kPa 条件下， 反应 0.25h， 以80%的产率得到[1,3-(SiMe₃)₂C₃H₃]^-₂Ni(CO)
  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：

  bis(acetylacetonate)nickel(II) 、 (1,3-bis(trimethylsilyl)allyl)potassium 以 四氢呋喃 为溶剂， 以41.2%的产率得到[1,3-(SiMe₃)₂C₃H₃]^-₂Ni
  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

• Reactivity of Silyl-Substituted Allyl Compounds with Group 4, 5, 9, and 10 Metals:  Routes to η³-Allyls, Alkylidenes, and <i>s</i><i>ec</i>-Alkyl Carbocations
  作者：Mark Schormann、Shaun Garratt、Manfred Bochmann

  DOI：10.1021/om0491692

  日期：2005.3.1

  E+[C3H3(SiMe3)2-1,3]- (E = Li, K) with group 4 and group 5 metal halides gave intractable reduction products, Co(acac)3 and Ni(acac)2 reacted with K[C3H3(SiMe3)2-1,3] to give Coη3-C3H3(SiMe3)2-1,3}2 (1) and Niη3-C3H3(SiMe3)2-1,3}2 (2), respectively. The reaction of K[C3H3(SiMe3)2-1,3] with Me3SnCl afforded Me3SiCHCHCH(SiMe3)(SnMe3) (3), which reacted cleanly with TaCl5 to give η3-C3H3(SiMe3)2-1,3}TaCl4

  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
• Trimethylsilylated Allyl Complexes of Nickel. The Stabilized Bis(π-allyl)nickel Complex [η³-1,3-(SiMe₃)₂C₃H₃]₂Ni and Its Mono(π-allyl)NiX (X = Br, I) Derivatives
  作者：Keith T. Quisenberry、J. Dominic Smith、Markus Voehler、Donald F. Stec、Timothy P. Hanusa、William W. Brennessel

  DOI：10.1021/ja044308s

  日期：2005.3.1

  theory calculations performed on the bis(allyl)nickel complexes indicate that the substituents exert little effect on the basic metal-ligand geometries. Trimethylphosphine is converted to tetramethyltetraphosphane, (MeP)4, on reaction with 1. In toluene, 3-bromo-1,3-bis(trimethylsilyl)propene reacts with (COD)2Ni to produce the dimeric purple complex [1,3-(SiMe3)2C3H3]NiBr}2 (2a). Both NMR and X-ray

  在-78 摄氏度的 THF 中，2 当量的 K[1,3-(SiMe3)2C3H3] 与 NiBr2(dme) 反应生成橙色 pi-烯丙基复合物 [1,3-(SiMe3)2C3H3]2Ni (1)。与自燃的 (C3H5)2Ni 不同，三甲基甲硅烷基化衍生物仅在空气中缓慢分解（从数小时到数天）。在溶液中发现了重叠 (1a) 和交错 (1b) 构象；当加热到 85 摄氏度以上时，黯淡的形式不可逆地转化为热力学上更稳定的交错构象。 1a 和 1b 的单晶 X 射线结构证实烯丙基配体以三联体方式与金属结合，并且三甲基甲硅烷基取代基是同步的，反安排的。对双（烯丙基）镍配合物进行的密度泛函理论计算表明，取代基对基本金属配体几何结构影响很小。三甲基膦与 1 反应后转化为四甲基四膦 (MeP)4。在甲苯中，3-溴-1,3-双（三甲基甲硅烷基）丙烯与 (COD)2Ni 反应生成二聚紫色复合物 [1,3- (SiMe3)2C3H3]NiBr}2