phenyldioctylsilane | 18752-54-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: phenyldioctylsilane
• 英文别名: Ph(octyl)2SiH；Dioctyl(phenyl)silane
• CAS: 18752-54-0
• 化学式: C₂₂H₄₀Si
• 分子量: 332.645
• InChiKey: OVRWOJSJXRBZJI-UHFFFAOYSA-N

物化性质

• 沸点：
  200-223 °C(Press: 22 Torr)
• 密度：
  0.8704 g/cm3(Temp: 25 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  6.84
• 重原子数：
  23
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  phenyldioctylsilane 、 1-triethylsilyl-2-octene 在 [(2,6-Me2PDI)FeN2]2(µ2-N2) 作用下， 生成 C₃₆H₇₀Si₂
  参考文献：
  名称：

  SATURATED AND UNSATURATED SILAHYDROCARBONS VIA IRON AND COBALT PYRIDINE DIIMINE CATALYZED OLEFIN SILYLATION

  摘要：

  本发明涉及使用含铁或含钴催化剂合成饱和和不饱和硅烃的过程。该发明的过程可以生产四烷基硅烷、苯基三烷基硅烷、取代苯基三烷基硅烷及其混合物，这些对润滑剂和液压油很有用，以及烷基烯基硅烷、苯基烯基硅烷和取代苯基烯基硅烷及其混合物，这些对合成饱和硅烃和其他有机官能硅烷很有用。

  公开号：

  US20140330036A1
• 作为产物：
  描述：

  辛烯 、 苯硅烷 在 iron(II) tetrafluoroborate hexahydrate 、 2,6-bis[1-((2,6-diethylphenyl)imino)ethyl]pyridine 作用下， 以 四氢呋喃 为溶剂， 反应 3.5h， 以87%的产率得到phenyldioctylsilane
  参考文献：
  名称：

  区域发散的氢化硅烷化，氢化，[2π+2π]-环加成反应和使用抗衡离子活化的土壤富集金属催化的C–H硼化†

  摘要：

  由于产生活性低氧化态催化剂所需的通常具有挑战性的实际要求，富含地球的金属催化的广泛采用落后于第二行和第三行的过渡金属。在这里，我们报告了使用铁和钴的预催化剂跨越五个反应类别的单一内源性活化方案的发展。这种简单的催化歧管使用市售的板凳稳定的四氟硼酸铁或钴盐进行区域发散性的烯烃和炔烃氢化硅烷化，1,3-二烯氢化硅烷化，氢化，[2π+2π]-环加成和CHH硼化。通过氟化物从抗衡离子上解离，原位形成氢化活化剂并生成低氧化态催化剂来进行活化。

  DOI：

  10.1039/c8sc05391j

文献信息

• Cationic Nickel(II)-Catalyzed Hydrosilylation of Alkenes: Role of P, N-Type Ligand Scaffold on Selectivity and Reactivity
  作者：Istiak Hossain、Joseph A. R. Schmidt

  DOI：10.1021/acs.organomet.0c00551

  日期：2020.9.28

  Seven structurally similar cationic nickel(II)–alkyl complexes were synthesized by using a series of P, N ligands, and their reactivity was explored in the hydrosilylation of alkenes. More electron-rich phosphines enhanced the overall reactivity of the transformation; in contrast, groups on the imine donor had little impact. Overall, these catalysts displayed reactivity and selectivity that was previously

  使用一系列P，N配体合成了七个结构相似的阳离子镍（II）-烷基络合物，并在烯烃的氢硅烷化中探索了它们的反应性。更多的富电子膦提高了转化的整体反应性；相反，亚胺供体上的组几乎没有影响。总体而言，这些催化剂显示出在镍催化的氢化硅烷化中以前未知或非常罕见的反应性和选择性。在与Ph 2 SiH 2的反应中，1,2-二取代的乙烯基芳烃显示出对硅烷加成的完全苄基选择性，而对1,1-二取代的烯烃则观察到末端选择性。相关的PhSiH 3导致仅对单个取代的乙烯基芳烃进行马尔可夫尼科夫选择性，而未观察到竞争的双加成。机理研究支持以下假设：Ni-H在此催化氢硅烷化反应中充当活性物质，这反过来也显示了硅烷再分布反应的催化能力，特别是对于空间不受阻的硅烷。
• Nickel-Catalyzed Hydrosilylation of Terminal Alkenes with Primary Silanes via Electrophilic Silicon–Hydrogen Bond Activation
  作者：Xiaoyu Wu、Guangni Ding、Wenkui Lu、Liqun Yang、Jingyang Wang、Yuxuan Zhang、Xiaomin Xie、Zhaoguo Zhang

  DOI：10.1021/acs.orglett.1c00111

  日期：2021.2.19

  NiCl2·6H2O/tBuOK, for the electrophilically activated hydrosilylation of terminal alkenes with primary silanes. This protocol provides excellent performance under mild reaction conditions: exclusive anti-Markovnikov selectivity, broad functional group tolerance (36 examples), and good scalability (TON = 5500). However, the secondary and tertiary silanes are not suitable. Mechanistic studies revealed that

  我们报告了一种简单有效的镍基催化体系NiCl 2 ·6H 2 O / t BuOK，用于末端烯烃与伯硅烷的亲电子活化氢化硅烷化。该方案在温和的反应条件下具有出色的性能：独特的抗马尔科夫尼科夫选择性，宽泛的官能团耐受性（36个示例）和良好的可扩展性（TON = 5500）。但是，仲和叔硅烷是不合适的。机理研究表明，这种均相催化的硅氢加成反应包括一种亲电子活化的Si-H键过程，而不会产生氢化镍。
• Tuning the redox non-innocence of a phenalenyl ligand toward efficient nickel-assisted catalytic hydrosilylation
  作者：Gonela Vijaykumar、Anand Pariyar、Jasimuddin Ahmed、Bikash Kumar Shaw、Debashis Adhikari、Swadhin K. Mandal

  DOI：10.1039/c7sc04687a

  日期：——

  hydrosilylation has been investigated. A phenalenyl ligand coordinated nickel complex has been utilized as an electron reservoir to develop a base metal-assisted catalyst, which very efficiently hydrosilylates a wide variety of olefin substrates under ambient conditions. A mechanistic investigation revealed that a two-electron reduced phenalenyl based biradical nickel complex plays the key role in such catalysis

  在该报告中，已经研究了配体-氧化还原辅助的催化硅氢加成反应。苯甲烯基配位体配位的镍络合物已被用作电子储库，以开发贱金属辅助催化剂，该催化剂在环境条件下非常有效地将多种烯烃底物进行硅氢加成反应。机理研究表明，两电子还原的基于菲烯基的双自由基镍络合物在这种催化中起关键作用。使用EPR光谱，磁化率测量和使用DFT方法的电子结构计算已探究了具有催化活性的双自由基物质的电子结构。通过自由基淬灭剂抑制反应，以及沿着催化环对两种中间体进行质谱检测，提示从配体主链的单电子转移开始催化。利用配体的氧化还原储库性质的策略可确保镍不会被提升到不利的氧化态，并且在配体与金属氧化还原轨道之间的精细调节会引发平滑的催化作用。
• Catalytic Hydrosilylation of Alkenes by Iron Complexes Containing Terpyridine Derivatives as Ancillary Ligands
  作者：Kouji Kamata、Atsuko Suzuki、Yuta Nakai、Hiroshi Nakazawa

  DOI：10.1021/om300279t

  日期：2012.5.28

  Iron complexes formulated as Fe(terpy)X-2 (terpy = 2,2':6',2 ''-terpyridine derivatives; X = Cl, Br) were prepared and their catalytic activities for hydrosilylation of olefin with hydrosilane were examined. Although Fe(terpy)X-2 did not show catalytic activity, the treatment of Fe(terpy)X-2 with NaHBEt3 caused catalytic activity. The influence of substituents in terpy on the catalytic activity was examined, and it was found that some complexes with an unsymmetrically disubstituted terpy selectively produced 1-silylalkane with quite high catalytic activity. In the reaction of 1-octene with PhSiH3, the double-hydrosilylation product Ph(1-octyl)(2)SiH was selectively obtained.
• Hydrosilylation of Olefins Catalyzed by Iron Complexes Bearing Ketimine-Type Iminobipyridine Ligands
  作者：Yuki Toya、Kazumasa Hayasaka、Hiroshi Nakazawa

  DOI：10.1021/acs.organomet.7b00087

  日期：2017.5.8

  A series of NNN-pincer iron complexes bearing ketimine-type iminobipyridene (BPI) ligands were prepared.. These iron complexes were effective catalysts for the hydrosilylation of olefins using primary, secondary, and tertiary silanes. The effect of the substituents on the imino carbon on the catalytic activity was examined, and it was found that an appropriate combination of the imino carbon and imino nitrogen substituents led to complexes with quite high catalytic activity: the turnover number achieved was up to 42000. These iron catalytic systems provide a low-cost and promising alternative to currently employed precious metal systems for the hydrosilylation of olefins.