diphenyl[2-(triphenylsilyl)ethyl]phosphane | 76734-21-9

• 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: diphenyl[2-(triphenylsilyl)ethyl]phosphane
• 英文别名: Triphenylsilylethyl Diphenyl Phosphine；diphenyl(2-triphenylsilylethyl)phosphane
• CAS: 76734-21-9
• 化学式: C₃₂H₂₉PSi
• 分子量: 472.642
• InChiKey: IIHWUHQYPQSWRK-UHFFFAOYSA-N

物化性质

• 沸点：
  564.0±42.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.29
• 重原子数：
  34
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  乙烯双(三苯基磷)铂 、 diphenyl[2-(triphenylsilyl)ethyl]phosphane 以 苯 为溶剂， 以52%的产率得到
  参考文献：
  名称：

  过渡金属甲硅烷基络合物。59. 1对未激活的Si-C键的氧化加成至Platinum（0）中心

  摘要：

  博士的反应2 PCH 2 CH 2 SIPH 3 - ñ我Ñ（Ñ = 0，1），（PH 3 P）2铂（π-C 2 H ^ 4）在形成升高的温度下的结果通过氧化加成的Si-C苯基。没有观察到Si-Me基团的氧化加成。因此，用Ph 2 PCH 2 CH 2 SiMe 3不能得到螯合物。当PEt 3和Ph 2 PCH的混合物形成复合物时2 CH 2 SIPH 2 Me为与反应（PH 3 P）2铂（π-C 2 H ^ 4）。

  DOI：

  10.1021/om9805335
• 作为产物：
  描述：

  二苯基膦 、 乙烯基三苯基硅烷 以 环己烷 为溶剂， 生成 diphenyl[2-(triphenylsilyl)ethyl]phosphane
  参考文献：
  名称：

  Trihydrocarbyl silyl substituted alkyl diaryl phosphine transition metal

  摘要：

  本发明涉及一种使用新型均相三氢基烷基二芳基膦过渡金属配合物的羰基化过程，其通式为：[(Ar.sub.2 PQ).sub.y SiR.sub.4 -y].sub.g (MX.sub.n).sub.s，其中Ar是C.sub.6到C.sub.10芳香烃基，Q是C.sub.1到C.sub.30饱和直链二价基团，R是C.sub.1到C.sub.10烃基，其中Ar、Q和R可以是取代或未取代的，y为1到4，g乘以y为1到6，M是从第VIII族过渡金属中选择的过渡金属，X是阴离子或有机配体，不包括卤素，满足金属的价和配位位点，n为2到6，s为1到3。这些材料具有高热稳定性，并且是选择性烯烃羰基化的优良催化剂，特别是在存在过量的配体[(Ar.sub.2 PQ).sub.y SiR.sub.4 -y]的情况下。具体而言，三（三甲基硅基）乙基二苯基膦铑羰基氢化物[(CH.sub.3).sub.3 Si--CH.sub.2 CH.sub.2 -PPh.sub.2 ].sub.3 Rh(CO)H和三[双（二苯基膦基）乙基]二甲基硅烷铑羰基氢化物[(CH.sub.3).sub.2 Si--CH.sub.2 CH.sub.2 -PPh.sub.2 ].sub.3 Rh(CO)H是选择性烯烃羰基化催化剂，特别是在过量三氢基烷基二芳基膦配体的存在下。

  公开号：

  US04480137A1

文献信息

• Visible Light-Driven Radical <i>trans</i>-Hydrosilylation of Electron-Neutral and -Rich Alkenes with Tertiary and Secondary Hydrosilanes
  作者：Jing Zhu、Wei-Chen Cui、Shaozhong Wang、Zhu-Jun Yao

  DOI：10.1021/acs.joc.8b02409

  日期：2018.12.7

  regio-, and stereoselective manner. Comparison of the reactivity of diene compounds and late-stage hydrosilylation of steroid drugs were also explored. Deuterium labeling experiments reveal that a stepwise formation of C–Si and C–H bonds with a trans stereochemistry is preferred, in which the thiol may behave as a hydrogen atom transfer agent.

  在新开发的由曙红Y，硫醇和碱添加剂组成的催化反应体系的基础上，研究了电子中性和富含烯烃的可见光驱动的自由基硅氢加成反应。发现具有不同取代模式的各种线性和环状烯烃以化学，区域和立体选择性方式与叔和仲氢硅烷进行这种无金属的氢化硅烷化。还研究了二烯化合物的反应性和类固醇药物的后期氢化硅烷化的比较。氘标记实验表明，以反式立体化学逐步形成C–Si和C–H键是可取的，其中硫醇可能起氢原子转移剂的作用。
• Transition metal complex catalysts
  申请人：Exxon Research and Engineering

  公开号：US04668809A1

  公开（公告）日：1987-05-26

  Compositions of matter are disclosed which are highly useful in hydroformylation processes. The compositions are non-charged, non-chelated bis- and tris-(alkyl diaryl phosphine) rhodium carbonyl hydrides. The substituents of the alkyl group includes heteroorganic radicals containing ether, ester, keto and hydroxy oxygen, phosphine oxide and phosphorus ester phosphorus, amine, amide, amine oxide and heterocyclic nitrogen groups. These compositions are highly stable and selective catalysts for the hydroformylation of olefins under certain conditions. The disclosed catalyst systems contain a large excess of phosphine ligand and employ alpha-olefin plus synthesis gas reactant mixtures having a high H.sub.2 /CO ratio at relatively low pressures. They produce moslty aldehydes derived from terminal attack on the alpha-olefin reactant. In the case of low olefins, such as butene-1, the products can be advantageously removed in a continuous manner, as distillate components from a ligand reaction mixture kept at an elevated temperature and continuously fed by an appropriate mixture of the reactants.

  本发明披露了一种在氢甲酰化过程中非常有用的物质组成物。该组成物是非带电、非螯合的双(烷基二芳基膦)、三(烷基二芳基膦)铑羰基氢化物。烷基基团的取代基包括含有醚、酯、酮和羟基氧、膦氧和磷酸酯磷、胺、酰胺、胺氧和杂环氮基的杂有机基团。这些组成物是高度稳定和选择性的催化剂，可在一定条件下用于烯烃的氢甲酰化反应。披露的催化剂体系含有大量的膦配体，并采用具有高H.sub.2/CO比的α-烯烃加合物和合成气反应物混合物，在相对较低的压力下。它们主要产生从α-烯烃反应物的末端攻击中得到的醛。对于低烯烃，例如丁烯-1，可以从保持在高温下并由适当的反应物混合物连续供给的配体反应混合物中以馏分组分的形式优势地去除产物。
• Ligand exchange process for producing alkyl diaryl phosphine rhodium
  申请人：Exxon Research and Engineering Company

  公开号：US04687866A1

  公开（公告）日：1987-08-18

  Compositions of matter are disclosed which are highly useful in hydroformylation processes. The compositions are non-charged, non-chelated bis- and tris-(alkyl diaryl phosphine) rhodium carbonyl hydrides. The substituents of the alkyl group include heteroorganic radicals containing silane, silicone, ether, ester, keto and hydroxy oxygen, phosphine oxide and phosphorus ester phosphorus, amine, amide, amine oxide and heterocyclic nitrogen groups. These compositions are highly stable and selective catalysts for the hydroformylation of olefins under certain conditions. The disclosed catalyst systems contain a large excess of phosphine ligand and employ alpha-olefin plus synthesis gas reactant mixtures having a high H.sub.2 /CO ratio at relatively low pressures. They produce mostly aldehydes derived from terminal attack on the alpha-olefin reactant. In the case of low olefins, such as butene-1, the products can be advantageously removed in a continuous manner, as distillate components from a ligand reaction mixture kept at an elevated temperature and continuously fed by an appropriate mixture of the reactants.

  披露了在水合甲酰化过程中非常有用的物质组成物。这些组成物是非带电、非螯合的双(烷基二芳基膦)和三(烷基二芳基膦)铑羰基氢化物。烷基基团的取代基包括含有硅烷、硅氧烷、醚、酯、酮和羟基氧、膦氧和磷酸酯磷的杂有机基团、胺、酰胺、胺氧和杂环氮基团。这些组成物是高度稳定和选择性催化剂，在一定条件下用于烯烃的水合甲酰化反应。所披露的催化剂体系含有大量的膦配体，并使用具有高H.sub.2/CO比的α-烯烃和合成气反应物混合物，在相对较低的压力下。它们主要产生由α-烯烃反应物的末端攻击产生的醛。对于低烯烃，例如丁烯-1，可以从保持在高温下并由适当的反应物混合物连续供给的配体反应混合物中优势地连续地去除产物，作为馏分组分。
• Selective hydroformylation process using alkyl diaryl phosphine rhodium
  申请人：Exxon Research and Engineering Company

  公开号：US04687874A1

  公开（公告）日：1987-08-18

  Compositions of matter are disclosed which are highly useful in hydroformylation processes. The compositions are non-charged, non-chelated bis- and tris-(alkyl diaryl phosphine) rhodium carbonyl hydrides. The substituents of the alkyl group include heteroorganic radicals containing ether, ester, keto and hydroxy oxygen, phosphine oxide and phosphorus ester phosphorus, amine, amide, amine oxide and heterocyclic nitrogen groups. These compositions are highly stable and selective catalysts for the hydroformylation of olefins under certain conditions. The disclosed catalyst systems contain a large excess of phosphine ligand and employ alpha-olefin plus synthesis gas reactant mixtures having a high H.sub.2 /CO ratio at relatively low pressures. They produce mostly aldehydes derived from terminal attack on the alpha-olefin reactant. In the case of low olefins, such as butene-1, the products can be advantageously removed in a continuous manner, as distillate components from a ligand reaction mixture kept at an elevated temperature and continuously fed by an appropriate mixture of the reactants.

  本发明揭示了一种在加氢甲酰化过程中非常有用的物质组成物。这些组成物是非带电的、非螯合的双(烷基二芳基膦)和三(烷基二芳基膦)钌羰基氢化物。烷基基团的取代基包括含有醚、酯、酮和羟基氧、膦氧和磷酸酯磷、胺、酰胺、胺氧和杂环氮基的杂有机基团。这些组成物是高度稳定和选择性的催化剂，在特定条件下对烯烃的加氢甲酰化反应非常有效。揭示的催化剂系统包含大量过量的膦配体，并使用具有高H.sub.2/CO比的α-烯烃加合物和合成气反应混合物，在相对较低的压力下进行。它们主要产生从α-烯烃反应物的端部攻击中得到的醛类产物。在低烯烃（如丁烯-1）的情况下，可以从保持在升高温度下并通过适当的反应物混合物连续供给的配体反应混合物中作为馏分组分优势地去除产物。
• Homogeneous hydroformylation catalysis with silyl substituted alkyl
  申请人：Exxon Research and Engineering Co.

  公开号：US04450299A1

  公开（公告）日：1984-05-22

  Described is a carbonylation process using novel homogeneous trihydrocarbyl silyl-substituted alkyl diaryl phosphine transition metal complexes of the general formula: [(Ar.sub.2 PQ).sub.y SiR.sub.4 -y].sub.g (MX.sub.n).sub.s wherein Ar is a C.sub.6 to C.sub.10 aromatic hydrocarbyl radical, Q is a C.sub.1 to C.sub.30 saturated straight chain divalent radical, R is a C.sub.1 to C.sub.10 hydrocarbyl, wherein Ar, Q and R, can be substituted or unsubstituted, y is 1 to 4, g times y is 1 to 6, M is a transition metal selected from the group consisting of Group VIII transition metals, X is an anion or organic ligand excluding halogen satisfying the valence and coordination sites of the metal, n is 2 to 6 and s is 1 to 3, are disclosed. These materials exhibit high thermal stability and are superior catalysts for the selective hydroformylation of olefins, particularly in the presence of excess quantities of ligand of the formula: (Ar.sub.2 PQ).sub.y SiR.sub.4-y wherein Ar, Q, R, and y are as previously defined. Specifically, tris-(trimethyl silyl-ethyl diphenyl phosphine) rhodium carbonyl hydride, [(CH.sub.3).sub.3 Si--CH.sub.2 CH.sub.2 --PPh.sub.2 ].sub.3 Rh(CO)H and tris [bis-(diphenylphosphinoethyl)dimethylsilane] rhodium carbonyl hydride, [(CH.sub.3).sub.2 Si--CH.sub.2 CH.sub.2 --PPh.sub.2 ].sub.3 Rh(CO)H, are selective olefin hydroformulation catalysts, particularly in the presence of excess trihydrocarbyl silyl-substituted alkyl diaryl phosphine ligand.

  本文介绍了一种使用新型均相三羟基烷基取代的烷基二芳基膦过渡金属配合物的羰基化过程，其一般公式为：[(Ar.sub.2 PQ).sub.y SiR.sub.4 -y].sub.g (MX.sub.n).sub.s，其中Ar为C.sub.6到C.sub.10芳香烃基，Q为C.sub.1到C.sub.30饱和直链二价基团，R为C.sub.1到C.sub.10的烃基，其中Ar、Q和R可以被取代或未取代，y为1到4，g乘以y为1到6，M为从第八族过渡金属中选出的过渡金属，X为阴离子或有机配体，不包括卤素，满足金属的价和配位位点，n为2到6，s为1到3。这些材料具有高热稳定性，并且是选择性烯烃羰基化反应的优良催化剂，特别是在存在过量的配体的情况下，其配体的公式为：(Ar.sub.2 PQ).sub.y SiR.sub.4-y，其中Ar、Q、R和y如前所述。具体来说，三(三甲基硅基乙基二苯基膦)铑羰基氢化物，[(CH.sub.3).sub.3 Si--CH.sub.2 CH.sub.2 --PPh.sub.2 ].sub.3 Rh(CO)H和三[双(二苯基膦基乙基)二甲基硅烷]铑羰基氢化物，[(CH.sub.3).sub.2 Si--CH.sub.2 CH.sub.2 --PPh.sub.2 ].sub.3 Rh(CO)H，是选择性烯烃羰基化反应的催化剂，特别是在存在过量三羟基烷基取代的烷基二芳基膦配体的情况下。