Trimethylsilylmethyl-diphenylphosphinsulfid | 4451-97-2

• 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: Trimethylsilylmethyl-diphenylphosphinsulfid
• 英文别名: Diphenyl-sulfanylidene-(trimethylsilylmethyl)-lambda5-phosphane；diphenyl-sulfanylidene-(trimethylsilylmethyl)-λ5-phosphane
• CAS: 4451-97-2
• 化学式: C₁₆H₂₁PSSi
• 分子量: 304.468
• InChiKey: QCVHMFZVUYQMGO-UHFFFAOYSA-N

物化性质

• 熔点：
  89.5 °C
• 沸点：
  385.8±44.0 °C(Predicted)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  32.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Trimethylsilylmethyl-diphenylphosphinsulfid 在 正丁基锂 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  非柱塞型单核Scan亚烷基络合物：合成，键合和反应性

  摘要：

  合成了第一个非钳型单核alkyl亚烷基络合物并进行了结构表征。这些配合物表现出较短的Sc-C键长度，甚至是迄今报道的最短的键之一（2.1134（18）Å）。通过DFT计算可以突出显示Sc-C键的多重特征。实验性反应性研究证实了这一点，其中该复合物与元素硒进行了[2 + 1]环加成，与亚胺进行了[2 + 2]环加成。DFT计算还揭示了亚烷基络合物的强亲核行为，这是通过苯乙炔的C-H键活化实验证明的。

  DOI：

  10.1002/chem.201504725
• 作为产物：
  描述：

  二苯基氯化膦 在 sulfur 作用下， 以 乙醚 为溶剂， 生成 Trimethylsilylmethyl-diphenylphosphinsulfid
  参考文献：
  名称：

  Synthesis of compounds containing phosphorus and silicon

  摘要：

  DOI：

  10.1007/bf00845591

文献信息

• Rhodium (Thiophosphinoyl)(trimethylsilyl)methanide and Bis(thiophosphinoyl)methanide Complexes: S~S vs. C~S Coordination
  作者：Hadrien Heuclin、Sophie Carenco、Xavier‐Frédéric Le Goff、Nicolas Mézailles

  DOI：10.1002/ejic.201101073

  日期：2012.3

  study of the coordination modes of a (thiophosphinoyl)(trimethylsilyl)methanide (1–·Li+) and bis(thiophosphinoyl)methanide (2–·Li+) ligand with RhI was carried out. Several complexes were synthesized and characterized. For 1–·Li+, C~S coordination is forced, whereas for 2–·Li+, S~S and C~S coordination can be achieved. In one case, a dynamic equilibrium between these two modes of coordination was observed

  对（硫代膦酰基）（三甲基甲硅烷基）甲烷化物（1-·Li+）和双（硫代膦酰基）甲烷化物（2-·Li+）配体与 RhI 的配位模式进行了比较研究。合成并表征了几种配合物。对于1-·Li+，强制C~S配位，而对于2-·Li+，可以实现S~S和C~S配位。在一种情况下，观察到这两种协调模式之间的动态平衡。进行 DFT 计算以合理化这种现象和甲烷化合物的稳定性。
• Substitution Effects on the Formation of T-Shaped Palladium Carbene and Thioketone Complexes from Li/Cl Carbenoids
  作者：Sebastian Molitor、Kai-Stephan Feichtner、Claudia Kupper、Viktoria H. Gessner

  DOI：10.1002/chem.201304927

  日期：2014.8.18

  contrast, insufficient charge stabilization results in the transfer of the sulfur of the thiophosphoryl moiety and thus in the formation of a thioketone complex. While the thioketones are stable compounds the carbene complexes are revealed to be highly reactive and decompose under elimination of Pd metal. Computational studies revealed that both complexes are formed by a substitution mechanism. While

  用Pd 0处理硫代磷酰基取代的Li / Cl类胡萝卜素制备钯硫酮和T形卡宾配合物报告了前体。根据空间需求，甲硅烷基部分的负离子稳定能力（通过负超共轭效应）和在羧基碳原子上剩余的负电荷，可以分离出三坐标的T形钯卡宾配合物。相反，不足的电荷稳定化导致硫代磷酰基部分的硫的转移并因此导致硫酮配合物的形成。尽管硫酮是稳定的化合物，但卡宾络合物显示出高反应性，并且在消除Pd金属后会分解。计算研究表明，两种复合物都是通过取代机制形成的。虽然发现酮是热力学上有利的产物，但是卡宾是动力学上有利的，因此优选在低反应温度下形成。
• Carbonyl olefination reaction using silyl-substituted organometallic compounds
  作者：Donald John Peterson

  DOI：10.1021/jo01266a061

  日期：1968.2
• Synthesis of Phosphorus(V)-Stabilized Geminal Dianions. The Cases of Mixed P═X/P→BH₃ (X = S, O) and P═S/SiMe₃ Derivatives
  作者：Hadrien Heuclin、Marie Fustier-Boutignon、Samuel Ying-Fu Ho、Xavier-Frédéric Le Goff、Sophie Carenco、Cheuk-Wai So、Nicolas Mézailles

  DOI：10.1021/om300954a

  日期：2013.1.28

  The monodeprotonation of [CH2(PPh2 -> BH3)(PPh2=E)] (E = S (6), O (7)) afforded [CH(PPh2 -> BH3)(PPh2=-E)](-) (E = S (6(-)), O (7(-))), whose structures were confirmed by X-ray crystallography. The kinetics of the second deprotonation appeared to be crucial in efficient synthesis of the corresponding dianions. Thus, the double deprotonation of 6 only led to 6(2-); the analogous reaction with 7 was slower and resulted only in the partial formation of 7(2-). Double deprotonation of the compound [CH2(SiMe3)-(PPh2=S)] (8) also resulted in the partial formation of (C(SiMe3)(PPh2=S)](2-) (8(2-)), whose structure was confirmed by X-ray crystallography. The rare monomeric Mg carbene compound [MgC(PPh2 -> BH3)(PPh2=S)] (9) was obtained by the reaction of 6 with Mg(nBu)(2). The X-ray structure of 9 is presented.
• Formation of a Palladium Thioketone Complex from a Thiophosphinoyl Stabilized Li/Cl Carbenoid
  作者：Viktoria H. Gessner

  DOI：10.1021/om200584h

  日期：2011.8.22

  An in situ generated thiophosphinoyl stabilized Li/Cl carbenoid reacts with Pd(PPh3)(4) with formation of a palladium thioketone complex. The presence of both the thiophosphinoyl and silyl groups as anion-stabilizing substituents is insufficient to stabilize the expected alkylidene complex and instead results in a rearrangement to the thioketone compound.