bis[2-(dimethylsilylmethyl)phenyl]-phenylphosphane | 1449716-34-0

• 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: bis[2-(dimethylsilylmethyl)phenyl]-phenylphosphane
• CAS: 1449716-34-0
• 化学式: C₂₄H₃₁PSi₂
• 分子量: 406.655
• InChiKey: JDEWBYREASURRH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.58
• 重原子数：
  27.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  bis[2-(dimethylsilylmethyl)phenyl]-phenylphosphane 以 氘代甲苯 、 甲苯 为溶剂， 20.0 ℃ 、303.99 kPa 条件下， 反应 12.5h， 生成 [Pt{PhP((o-C₆H₄) CH₂SiMe₂)₂}(CO)₂]
  参考文献：
  名称：

  方形平面铂配合物中反式二甲硅烷基配位的稳定化

  摘要：

  通过使用两种不同的多齿膦硅烷基配体，我们制备了两种铂络合物[Pt {PhP（（o -C 6 H 4）CH 2 SiMe 2）2 } PPh 3 ]（3）和[Pt {P（（o -C 6 H 4）CH 2 SiMe 2）2（o -C 6 H 4）CHSiMe 2）} PPh 3 ]（4）在围绕Pt（II）中心的典型正方形平面几何结构中表现出硅原子的反式构型。复杂4最初的配体的第三个硅原子通过亚甲基分子的分子内C–H活化得到了结果，并显示出无反应的C–H···Pt相互作用，这得到了溶液NMR数据和固态X射线衍射分析的支持。还讨论了3对小分子的反应性。在H 2和CO的情况下，相应的二酐[PtH 2 {PhP（（o -C 6 H 4）CH 2 SiMe 2）2 } PPh 3 ]（5）和二羰基[Pt {PhP（（o -C 6 H 4）CH 2 SiMe 2）2 }（CO）2 ]（6）配合物进行了表征

  DOI：

  10.1021/acs.organomet.7b00566
• 作为产物：
  描述：

  二甲基一氯硅烷 、 bis(o-tolyl)(phenyl)phosphine 在 正丁基锂 、 四甲基乙二胺 作用下， 以 正己烷 为溶剂， 反应 28.0h， 以83%的产率得到bis[2-(dimethylsilylmethyl)phenyl]-phenylphosphane
  参考文献：
  名称：

  Phosphinodi(benzylsilane) PhP{(o-C₆H₄CH₂)SiMe₂H}₂: A Versatile “PSi₂H_x” Pincer-Type Ligand at Ruthenium

  摘要：

  The synthesis of the new phosphinodi(benzylsilane) compound PhP{(O-C6H4CH2)SiMe2H}(2) (1) is :achieved in a one-pot reaction from the corresponding phenylbis(o-tolylphosphine). Compound 1.acts as a pincer type ligand capable of adopting different coordination modes at Ru through different.extents. of Si-H bond 'activation as demonstrated by a combination of X-ray diffraction analysis, density functional theory calculations, and multinuclear NMR Spectroscopy. Reaction of 1 with RuH2(H-2)(2)Cy-3)(2) (2) yields quantitatively [RuH2{eta(2)-(HSiMe2)-CH2-o- C6H4](2)PPh}(PCy3)] (3), a complex.Stabilized by two rare high order epsilon-agostic Si-H bonds and involved in terminal hydride/eta(2) -Si-H exchange processes. A small free energy of reaction (Delta(r)G(298) = +16.9 kJ mol(-1)) was computed for dihydrogen loss from 3 with concomitant formation of the 16-electron species [RuH{[eta(2)-(HSiMe2)-CH2-o-C6H4]PPh[CH2-o-C6H4SiMe2])(PCy3)] (4). Complex 4 features an unprecedented Si-29 NMR decoalescence process. The dehydrogenation process is frilly reversible under standard conditions (1 bar, 298 K).

  DOI：

  10.1021/ic400703r

文献信息

• A family of rhodium and iridium complexes with semirigid benzylsilyl phosphines: from bidentate to tetradentate coordination modes
  作者：María Vicky Corona-González、Julio Zamora-Moreno、Cynthia A. Cuevas-Chávez、Ernesto Rufino-Felipe、Emmanuelle Mothes-Martin、Yannick Coppel、Miguel A. Muñoz-Hernández、Laure Vendier、Marcos Flores-Alamo、Mary Grellier、Sylviane Sabo-Etienne、Virginia Montiel-Palma

  DOI：10.1039/c7dt00727b

  日期：——

  Ir) in a tetradentate or tridentate fashion, depending on the strict exclusion of water. The dimeric compounds [ClM(SiMe2CH2-o-C6H4)2P(o-C6H4-CH2SiMe2H)]2, 2Rh and 2Ir, feature a tetradentate coordination of the starting ligand with P and two Si atoms as well as a non-classical agostic Si–H group. The presence of adventitious water in the solvents leads to the formation of two new complexes [(μ2-Cl

  新的三苄基硅烷膦P （o -C 6 H 4 CH 2）SiMe 2 H} 3（1）的合成表明，从P（o- tolyl）3可以高产率进行。化合物1以四齿或三齿形式配位至Rh和Ir二聚体[MC1（COD）] 2（M = Rh，Ir），这取决于严格排除水的情况。二聚化合物[ClM（SiMe 2 CH 2 - o -C 6 H 4）2 P（o -C 6 H 4-CH 2森达2 H）] 2，2RH和2IR，设有起始配体与P和两个Si原子以及一种非经典agostic Si-H基四齿配位。的外来的水在溶剂中的引线的存在对两个新的复合物的形成[（μ 2 -Cl）2中号2（森达2 CH 2 - ö -C 6 ħ 4）2 P（ø -C 6 ħ 4 -CH 2 SiMe 2 OSiMe 2 CH 2- ø -C 6 ħ 4 - ）P（森达2 CH 2 - ö -C 6 ħ 4）2 ]，3Rh中和3IR，其特点
• Phosphinodi(benzylsilane) PhP{(<i>o</i>-C₆H₄CH₂)SiMe₂H}₂: A Versatile “PSi₂H_<i>x</i>” Pincer-Type Ligand at Ruthenium
  作者：Virginia Montiel-Palma、Miguel A. Muñoz-Hernández、Cynthia A. Cuevas-Chávez、Laure Vendier、Mary Grellier、Sylviane Sabo-Etienne

  DOI：10.1021/ic400703r

  日期：2013.9.3

  The synthesis of the new phosphinodi(benzylsilane) compound PhP(O-C6H4CH2)SiMe2H}(2) (1) is :achieved in a one-pot reaction from the corresponding phenylbis(o-tolylphosphine). Compound 1.acts as a pincer type ligand capable of adopting different coordination modes at Ru through different.extents. of Si-H bond 'activation as demonstrated by a combination of X-ray diffraction analysis, density functional theory calculations, and multinuclear NMR Spectroscopy. Reaction of 1 with RuH2(H-2)(2)Cy-3)(2) (2) yields quantitatively [RuH2eta(2)-(HSiMe2)-CH2-o- C6H4](2)PPh}(PCy3)] (3), a complex.Stabilized by two rare high order epsilon-agostic Si-H bonds and involved in terminal hydride/eta(2) -Si-H exchange processes. A small free energy of reaction (Delta(r)G(298) = +16.9 kJ mol(-1)) was computed for dihydrogen loss from 3 with concomitant formation of the 16-electron species [RuH[eta(2)-(HSiMe2)-CH2-o-C6H4]PPh[CH2-o-C6H4SiMe2])(PCy3)] (4). Complex 4 features an unprecedented Si-29 NMR decoalescence process. The dehydrogenation process is frilly reversible under standard conditions (1 bar, 298 K).
• Stabilization of Trans Disilyl Coordination at Square-Planar Platinum Complexes
  作者：Cynthia A. Cuevas-Chávez、Julio Zamora-Moreno、Miguel A. Muñoz-Hernández、Christian Bijani、Sylviane Sabo-Etienne、Virginia Montiel-Palma

  DOI：10.1021/acs.organomet.7b00566

  日期：2018.3.12

  phosphinosilyl ligands, we prepared the two platinum complexes [PtPhP((o-C6H4)CH2SiMe2)2}PPh3] (3) and [PtP((o-C6H4)CH2SiMe2)2(o-C6H4)CHSiMe2)}PPh3] (4) exhibiting a trans configuration of the silicon atoms in a typical square-planar geometry around a Pt(II) center. Complex 4 results from intramolecular C–H activation of a methylene moiety by the third silicon atom of the original ligand and displays

  通过使用两种不同的多齿膦硅烷基配体，我们制备了两种铂络合物[Pt PhP（（o -C 6 H 4）CH 2 SiMe 2）2 } PPh 3 ]（3）和[Pt P（（o -C 6 H 4）CH 2 SiMe 2）2（o -C 6 H 4）CHSiMe 2）} PPh 3 ]（4）在围绕Pt（II）中心的典型正方形平面几何结构中表现出硅原子的反式构型。复杂4最初的配体的第三个硅原子通过亚甲基分子的分子内C–H活化得到了结果，并显示出无反应的C–H···Pt相互作用，这得到了溶液NMR数据和固态X射线衍射分析的支持。还讨论了3对小分子的反应性。在H 2和CO的情况下，相应的二酐[PtH 2 PhP（（o -C 6 H 4）CH 2 SiMe 2）2 } PPh 3 ]（5）和二羰基[Pt PhP（（o -C 6 H 4）CH 2 SiMe 2）2 }（CO）2 ]（6）配合物进行了表征