bis(diphenylphosphinomethyl)dimethylsilane | 59557-18-5

• 物质功能分类: 有机原料 - 有机膦化合物
• 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(diphenylphosphinomethyl)dimethylsilane
• 英文别名: 2,2-dimethyl-2-sila-1,3-bis(diphenylphosphino)propane；2,2-dimethyl-1,3-bis(diphenylphosphino)-2-silapropane；Phosphine, [(dimethylsilylene)bis(methylene)]bis[diphenyl-；[diphenylphosphanylmethyl(dimethyl)silyl]methyl-diphenylphosphane
• CAS: 59557-18-5
• 化学式: C₂₈H₃₀P₂Si
• 分子量: 456.579
• InChiKey: YQHRQVQNJGVQEM-UHFFFAOYSA-N

物化性质

• 沸点：
  538.3±35.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.04
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  bis(diphenylphosphinomethyl)dimethylsilane 以 二氯甲烷 、 丙酮 为溶剂， 生成
  参考文献：
  名称：

  Palladium and Platinum Units Grafted on the Periphery of Carbosilane Dendrimers

  摘要：

  DOI：

  10.1002/1099-0682(200209)2002:9<2477::aid-ejic2477>3.0.co;2-u
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 碳酸氢钠 、 tetrafluoroboric acid dimethyl ether complex 作用下， 以 二氯甲烷 为溶剂， 以89%的产率得到bis(diphenylphosphinomethyl)dimethylsilane
  参考文献：
  名称：

  An efficient procedure for the synthesis of C-chiral bisphosphines

  摘要：

  A practical method for the synthesis of bisphosphines containing homochiral carbon backbones is described. This procedure entails sequential reaction of a homochiral ditosylate with the appropriate dialkyl- or diarylphosphine-borane anion followed by BH5 decomplexation mediated by HBF4 . OMe(2).

  DOI：

  10.1016/0040-4020(95)00390-t
• 作为试剂：
  描述：

  乙烯基乙酸 、 一氧化碳 在 bis(diphenylphosphinomethyl)dimethylsilane 、 palladium diacetate 、 三氟乙酸 作用下， 以 二乙二醇二甲醚 、 水 为溶剂， 105.0 ℃ 、5.0 MPa 条件下， 反应 12.0h， 生成 戊二酸 、 甲基丁二酸
  参考文献：
  名称：

  Palladium Complexes with Bulky Diphosphine Ligands as Highly Selective Catalysts for the Synthesis of (Bio-) Adipic Acid from Pentenoic Acid Mixtures.

  摘要：

  A series of sterically bulky diphosphines have been prepared, including P-2 = trans-1,2-bis[(di-tert-butylphosphino)methyllcydohexane (4), (2-methylenepropane1,3-diy1)bis(di-tert-butylphosphine) (5), bis[(di-tertbutylphosphino)methyl]dimethylsilane (6), and cis- and trans11,12-bis [ (di-tert-butylphosphino)methy1]-9,10-dihydro-9,10-ethanoanthracene (10 and 11). The corresponding palladium complexes of these ligands, P2Pd(CF3CO2)(2), have been synthesized and characterized. The solid-state structures of [Pd(4)(CF3CO2)(2)], [Pd(S)(CF3CO2)(2)], [Pd(6)(CF3CO2)(2)], and [Pd(11)(CF3CO2)(2)] were obtained by single-crystal X-ray diffraction and confirm the bidentate binding mode of the ligand and a square-planar coordination geometry with a minor distortion from the ideal. The diphosphines in combination -with Pd(OAc)(2) have been applied in the hydroxycarbonylation of a mixture of pentenoic acid isomers to produce adipic acid with high selectivity (in several cases >95%). The (regio)selectivity of the hydroxycarbonylation reaction is highly dependent on the P-2 diphosphine ligand structure, particularly the steric bulk of the substituents on the diphosphine donor and the P-Pd-P bite angle in the complexes, with respectively tertiary alkyl phosphine substituents (tert-butyl, adamantyl) and a C4 backbone P-Pd-P bite angle >100 degrees being the common features of highly adipic acid selective systems. It is suggested that the regioselectivity of hydroxycarbonylation becomes largely driven by the chelation of the carboxylic acid functionality of pentenoic acid substrates, when smaller size P substituents and/or when P-2 ligands with smaller bite angles (<100 degrees) are applied.

  DOI：

  10.1021/acs.organomet.5b00517

文献信息

• Multinuclear NMR Spectroscopic and X-ray Crystallographic Studies of a Series of Mercury(II) Complexes Containing the Bidentate Phosphine Ligand Ph₂PCH₂Si(CH₃)₂CH₂PPh₂ (L²)
  作者：Elmer C. Alyea、George Ferguson、Ram P. Shakya、Paul R. Meehan

  DOI：10.1021/ic9704243

  日期：1997.10.1

  [HgI(2)(Ph(2)PCH(2)Si(CH(3))(2)CH(2)PPh(2))] (1) crystallizes in the monoclinic space group P2(1)/n with a = 13.028(2) Å, b = 17.402(5) Å, c = 13.849(2) Å, beta = 90.635(14) degrees, V = 3139.5(11) Å(3), and Z = 4. The structure contains a tetrahedral mercury center with the phosphine ligand bound in a bidentate fashion: Hg-P 2.511(2), 2.515(2) Å; P-Hg-P 105.28(6) degrees. The complex [HgCl(2)](2).L(2)

  双齿膦配体Ph（2）PCH（2）Si（CH（3））（2）CH（2）PPh（2）（L（2）），1,3-双（二苯基膦基）丙烷的类似物（ dppp），与汞（II）盐配位以形成通式[HgX（2）.L（2）]的配合物（X = Cl，Br，I，NCS）。红外，拉曼和多核（（1）H，（13）C，（31）P，（199）Hg）NMR光谱研究表明，该配合物表现出四坐标拟四面体金属几何形状。[HgI（2）（Ph（2）PCH（2）Si（CH（3））（2）CH（2）PPh（2））]（1）在单斜空间群P2（1）/ n中结晶a = 13.028（2）Å，b = 17.402（5）Å，c = 13.849（2）Å，beta = 90.635（14）度，V = 3139.5（11）Å（3），Z =4。结构Hg-P 2.511（2），2.515（2）Å;含有四面体汞中心，膦配体以二齿形式结合。P-Hg-P 105.28（6）度。[HgCl（2）]（2）
• Chromium-Based Ethylene Tetramerization Catalysts Supported by Silicon-Bridged Diphosphine Ligands: Further Combination of High Activity and Selectivity
  作者：Le Zhang、Xuejiao Meng、Yanhui Chen、Chengang Cao、Tao Jiang

  DOI：10.1002/cctc.201600941

  日期：2017.1.9

  characterized. The Cr precatalyst supported by bis(diphenylphosphinomethyl)dimethylsilane achieved a high activity of 4.2×106 g (molCr h)−1 and a high selectivity of 78.44 % towards valuable 1‐octene by using methylcyclohexane as the solvent at an ethylene pressure of 4.0 MPa and 45 °C. An intramolecular β‐H transfer mechanism was proposed to explain the unequal molar proportions of cyclic C6 byproducts

  合成并表征了一系列硅桥联二膦（SBDP）配体。通过使用二甲基环己烷作为溶剂，在乙烯压力为2的条件下，由双（二苯基膦基甲基）二甲基硅烷负载的Cr预催化剂具有4.2×10 6  g（mol Cr  h）-1的高活性和对有价值的1-辛烯的高选择性78.44％。 4.0 MPa和45°C。提出了分子内β-H转移机制来解释环状C 6副产物的摩尔比例不相等。两种配合物的晶体结构数据证明，具有宽P-Cr-P咬合角的SBDP系统在乙烯四聚反应中也表现出优异的性能。
• An efficient procedure for the synthesis of electron rich bisphosphines containing homochiral backbones
  作者：Lydia McKinstry、Tom Livinghouse

  DOI：10.1016/s0040-4039(00)78531-5

  日期：1994.12

  An eminently practical method for the synthesis of homochiral bisphosphines is described. This procedure entails the sequential reaction of homochiral ditosylate with the appropriate dialkylphosphine-borane anion followed by BH3 decomplexation mediated by HBF4·OMe2.

  描述了合成高手性双膦的一种非常实用的方法。该方法需要高手性二甲苯磺酸酯与适当的二烷基膦-硼烷阴离子进行顺序反应，然后由HBF 4 ·OMe 2介导的BH 3分解。
• Ruthenium-Diphosphine-Catalyzed Allylation of Phenols: A <i>gem</i>-Dialkyl-Type Effect Induces High Selectivity toward O-Allylation
  作者：Jimmy A. van Rijn、Maxime A. Siegler、Anthony L. Spek、Elisabeth Bouwman、Eite Drent

  DOI：10.1021/om900832g

  日期：2009.12.28

  structure−performance relationship and gain mechanistic insight in the selective O-allylation of a phenol with allyl alcohol. It appears that catalysts containing bidentate phosphine ligands having geminal dialkyl substituents at the central atom of a C3-bridging group of the phosphine ligand are highly selective for O-allylation; apparently the presence of the substituents efficiently blocks the competitive and thermodynamically

  探索了一系列具有环戊二烯基和双齿膦膦配体的新型阳离子钌（II）配合物的催化性能，以建立催化剂与结构的性能关系，并在酚与烯丙醇的选择性O-烯丙基化反应中获得了机理性的见解。似乎含有具有双齿膦配体的催化剂孪位以C的中心原子的二烷基取代基3膦配体的-桥连基团对O-烯丙基化具有高度选择性；显然，取代基的存在有效地阻碍了竞争性和热力学上更有利的C-烯丙基化途径。看起来，固态的Ru（II）前体络合物的电子和结构性质与包含未取代的类似配体的络合物的电子和结构性质没有显着差异，而所得的催化剂表现出极大的催化性能。六小时后，具有未取代配体的复合物[RuCp（dpppmp）]（OTs）产生70％的苯酚转化率，对O-烯丙基化的选择性仅为27％，而复合物[RuCp（dppdmp）]（OTs）用二甲基取代的配体，六小时后得到60％的苯酚转化率和82％的O-烯丙基化选择性。结果表明偕二烷基取代基在C的中心碳3配体的桥
• Catalytic behavior tuning via structural modifications of silylated‐diphosphine Ni(II) complexes for ethylene selective dimerization
  作者：Jiadong Wang、Fakhre Alam、Qiqi Chang、Yanhui Chen、Tao Jiang

  DOI：10.1002/aoc.5722

  日期：2020.8

  in the scaffold of the CH3Si(CH2)n(PPh2)3 and Si(CH2PPh2)4‐type silylated diphosphine Ni(II) complex systems have a marked impact on their catalytic performance in selective ethylene dimerization. Ni(II)‐based precatalyst 1, bearing two methylene spacers in its framework, exhibited the highest catalytic activity of 1.29 × 108 g (molNi)‐1 h‐1, while precatalyst 3, with three methylene spacers, affords

  CH 3 Si（CH 2）n（PPh 2）3和Si（CH 2 PPh 2）4型甲硅烷基化二膦Ni（II）配合物骨架中的亚甲基间隔基和未配位的二苯基膦部分对它们在选择性乙烯二聚反应中的催化性能。基于Ni（II）的预催化剂1在其框架中带有两个亚甲基间隔基，表现出最高的催化活性1.29×10 8 g（mol Ni）-1 h -1，而预催化剂3，带有三个亚甲基间隔基，对C 4馏分具有最高的产物选择性（88％）。晶体学研究表明，前催化剂3采用单核二齿结合模式，并且其未配位的二苯基膦部分的空间约束可能成功地调整了催化剂的催化环境。通过改变配体/ Ni摩尔比，预催化剂4可以形成双核络合物并显示出高催化活性。预催化剂3的高C 4选择性已通过密度泛函理论（DFT）计算合理化，并发现与实验结果相符。该研究还表明，设计新的基于Ni（II）的配合物系统及其系统修饰可能会进一步为选择性乙烯低聚提供潜在的和工业上可行的催化剂体系。