Benzenesulfonylmethyl-diphenyl-sulfanylidene-lambda5-phosphane | 31126-46-2

• 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: Benzenesulfonylmethyl-diphenyl-sulfanylidene-lambda5-phosphane
• 英文别名: benzenesulfonylmethyl-diphenyl-sulfanylidene-λ5-phosphane
• CAS: 31126-46-2
• 化学式: C₁₉H₁₇O₂PS₂
• 分子量: 372.449
• InChiKey: YAVHBWYXMSDATE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  74.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Benzenesulfonylmethyl-diphenyl-sulfanylidene-lambda5-phosphane 在 甲基锂 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以73%的产率得到
  参考文献：
  名称：

  四面体与平面四坐标碳：磺酰基取代的甲乙二胺

  摘要：

  展平！据报道，磺酰基取代的膦硫醚具有单或双锂化作用。新型二硫代二甲双胍在典型的四面体和平面排列之间具有扭曲的碳环境（见图）。这种几何形状是由于给体功能的几何限制而引起的，可以用锂原子与sp 2杂化的甲烷化物碳的两种不同的键合模式来描述。

  DOI：

  10.1002/chem.201201369
• 作为产物：
  描述：

  甲基二苯基膦硫化物 在 劳森试剂 、 正丁基锂 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 反应 26.5h， 生成 Benzenesulfonylmethyl-diphenyl-sulfanylidene-lambda5-phosphane
  参考文献：
  名称：

  Synthesis and Electronic Structure of Carbene Complexes Based on a Sulfonyl-Substituted Dilithio Methandiide

  摘要：

  The application of a sulfonyl-substituted dilithio methandiide in the synthesis of carbene complexes was examined. In all cases, the metal carbon interaction was found to be highly polar with only small pi-contribution. Hence, the stability of these complexes was found to greatly rely on the coordination ability of the side-arms supporting the metal carbon interaction. As such, the sulfonyl moiety allowed the isolation of a carbene complex with the oxophilic zirconium, which is the first of its kind bearing no (bis)phosphonium ligand framework. On the contrary, complexes with the late transition metals ruthenium and palladium were found to be more labile due to the facile decoordination of the sulfonyl moiety. This results in the opening of a reactive coordination site at the metal center and hence in further reactions such as cyclometalation or sulfur transfer from the thiophosphoryl moiety to the carbenic carbon atom.

  DOI：

  10.1021/om5001277

文献信息

• On the structure and ambiphilicity of a sulfonyl substituted α-chloro lithium base
  作者：Julia Becker、Viktoria H. Gessner

  DOI：10.1039/c3dt52800f

  日期：——

  An α-chloro lithium base stabilised by a sulfonyl and thiophosphinoyl moiety was selectively prepared by lithiation of its protonated precursor and oxidation of the corresponding dilithio methandiide. The carbenoid-like compound was found to be remarkably stable even at room temperature and thus allowed for its spectroscopic characterisation in solution and in the solid state. Its ambiphilic nature was tested and compared with typical carbenoids both experimentally and by computational methods. The electronic stabilisation results in its thermal stability but considerably reduces the ambiphilic character limiting the reactivity patterns generally observed for lithium carbenoids.

  通过对其质子化前体进行锂化，并氧化相应的二锂甲烷二酰亚胺，可选择性地制备出由磺酰基和硫代膦酰基部分稳定的β-氯锂基。 发现这种类似羰基的化合物即使在室温下也非常稳定，因此可以在溶液和固态下进行光谱表征。 通过实验和计算方法测试了它的两亲性，并将其与典型的羰基化合物进行了比较。 电子稳定性的结果是其热稳定性，但大大降低了两亲性，从而限制了通常观察到的锂羰基化合物的反应性模式。