trimethylphosphine radical cation | 594-09-2

• 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 - 有机金属化合物 - 有机类金属化合物
• 英文名称: trimethylphosphine radical cation
• CAS: 594-09-2；29997-99-7
• 化学式: C₃H₉P
• 分子量: 76.0782
• InChiKey: SWTKNORDFVROOZ-UHFFFAOYSA-N

物化性质

• 熔点：
  -86 °C (lit.)
• 沸点：
  38-40 °C (lit.)
• 密度：
  0.738 g/mL at 20 °C (lit.)
• 闪点：
  −4 °F

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 危险等级：
  4.2
• 危险品标志：
  F,Xi
• 安全说明：
  S16,S26,S33,S36/37,S36/37/39,S62,S7/9,S9
• 危险类别码：
  R36/37/38,R11
• WGK Germany：
  3
• 海关编码：
  29319090
• 危险品运输编号：
  UN 1993 3/PG 2
• 危险类别：
  4.2
• 包装等级：
  I
• 危险标志：
  GHS02,GHS07,GHS08
• 危险性描述：
  H225,H302,H315,H319,H335,H351
• 危险性防范说明：
  P210,P280,P301 + P312 + P330,P305 + P351 + P338,P370 + P378,P403 + P235

制备方法与用途

简介

三甲基膦是体积最小的三级膦，是一种非常强的配体，能与许多金属如铁、钴、镍、铜、金、银、钯、铂、钙、铑、铝、钛等形成稳定的配合体。这些金属配合体可用做许多化学反应如聚合、催化氢化、羰基化、置换反应的催化剂；三甲基膦本身还是一个清洁的还原剂。

用途

三甲基膦还可以用作制备离子液体的原料。离子液体有着广阔的应用前景，如可用作化学反应的溶剂，电化学设施的电解质、抗静电剂、润滑剂等，三甲基膦还可被用作制做医药、农药等精细化工产品的中间体。

反应信息

• 作为反应物：
  描述：

  二甲基二硫 、 trimethylphosphine radical cation 以 gas 为溶剂， 生成 methylthio radical 、 Trimethyl(methylsulfanyl)phosphanium
  参考文献：
  名称：

  Unusual Reactivity of the Radical Cations of Some Simple Trivalent Organophosphorus Compounds toward Dimethyl Disulfide and Dimethyl Diselenide

  摘要：

  Dimethyl disulfide and dimethyl diselenide are known to readily undergo charge exchange with gaseous conventional radical cations containing oxygen, nitrogen, and sulfur functionalities. In sharp contrast, the radical cations of trimethylphosphine and trimethyl phosphite rapidly abstract CH3S. and CH3Se. groups from dimethyl disulfide and dimethyl diselenide, respectively, in a dual-cell Fourier-transform ion cyclotron resonance mass spectrometer, These sorts of abstraction reactions have been reported earlier only for distonic radical cations (ions with spatially separated charge and radical sites). Isomerization of the organophosphorus radical cations to their distonic forms prior to or during the reaction was ruled out by demonstrating that the connectivity in (CH3)(3)P-.+ does not change during the reaction: the CH3S. abstraction product has the structure (CH3P+-SCH3. Instead, the abstraction reactions are likely initiated by thermoneutral charge exchange. The neutral phosphorus compound then replaces a CH3S. or CH3Se. group in ionized dimethyl disulfide and ionized dimethyl diselenide, respectively, In support of this mechanism, three different neutral phosphorus compounds were shown to replace CH3S. in the radical cation of dimethyl disulfide. Phosphorus radical cations with high recombination energies were found to react with dimethyl disulfide by exclusive charge exchange, Hence, the abstraction reactions require a radical cation with a recombination energy close to the ionization energy of dimethyl disulfide (8.1 eV) and dimethyl diselenide (7.9 eV). Further, the reactions seem to be limited to phosphorus-containing ions since radical cations with nitrogen and sulfur functionalities do not undergo these reactions even when their recombination energies are close to 8.1 eV.

  DOI：

  10.1021/ja9531182
• 作为产物：
  描述：

  三甲基膦 以 various solvent(s) 为溶剂， 生成 trimethylphosphine radical cation
  参考文献：
  名称：

  三电子σ键自由基：氟利昂中R 3 P-Cl自由基的电子顺磁共振光谱研究

  摘要：

  我们的主要目的是要提请注意的三电子的相对稳定性σ键合的基团（σ 2 1，σ 1 2），大量的这种基团的已被研究了EPR spectroscopists，以及它们作为反应中间体的潜在重要性。该主题由实验其显示是当R所示3 P ˙+自由基阳离子（ME 3 P ˙+且Ph 3 P ˙+ ）以产生CFCL 3在77K通过暴露于60条钴γ射线，并且该系统退火到大约在155 K下，检测到具有R 3 P [Cl]基团的特征，并与31 P和35/37 Cl核定义良好的超精细偶联。认为这些一定是由电子捕获后从（CFCl 3）˙-自由基阴离子释放的氯离子形成的。

  DOI：

  10.1039/ft9908603293

文献信息

• Preparation and structure of certain phosphorus-centred radical cations. An electron spin resonance study
  作者：Akinori Hasegawa、Glen D. G. McConnachie、Martyn C. R. Symons

  DOI：10.1039/f19848001005

  日期：——

  60Co γ-rays at 77 K gave the corresponding cations, [·PL3]+, characterised by their e.s.r. spectra. The spectra establish that the SOMO for these cations is considerably localised on phosphorus, which contributes extensive atomic 3s and 3p character. The results confirm and extend previous studies using sulphuric acid matrices. The tendency for these cations to react with corresponding neutral molecules

  各种三价磷衍生物的稀溶液，PL的曝光3，在fluorotri氯甲烷到60个钴γ射线在77K，得到相应的阳离子，[·PL 3 ] +，其特征在于可以通过ESR光谱。光谱表明，这些阳离子的SOMO相当局限在磷上，这贡献了广泛的3 s和3 p原子特性。结果证实并扩展了以前使用硫酸基质的研究。这些阳离子与相应的中性分子反应以生成σ *二聚阳离子的趋势[L 3 P [图形省略] PL 3 ]+也被确认。
• Monomer and dimer cations of trimethylphosphine: a radiation chemical and e.s.r study
  作者：Martyn C. R. Symons、Glen D. G. McConnachie

  DOI：10.1039/c39820000851

  日期：——

  The 1H hyperfine coupling for Me3P˙+ ions generated radiolytically in freon at 77 K (ca. 11.5 G) is much greater than for the dimer cations (Me3P)2+(ca. 3.3 G): this is explained in terms of a decreasign tendency for σ–π delocalisation as the pyramidal character of the Me3P unit increases, coupled with a tendency towards σ-orbital localisation in σ*-radicals.

  的1个为我ħ超精细耦合3 P˙ +在77 K（在氟利昂radiolytically产生的离子约11.5 G）是远大于为二聚体阳离子（ME 3 P）2 +（约3.3克）：这是说明随Me 3 P单元的金字塔特征的增加，σ – π偏位的减少趋势，以及σ *自由基中σ轨道局部化的趋势。