tetrachloro-l5-phosphane | 20762-59-8

• 分子结构分类: 无机化合物
• 英文名称: tetrachloro-l5-phosphane
• 英文别名: phosphorus tetrachloride
• CAS: 20762-59-8
• 化学式: Cl₄P
• 分子量: 172.786
• InChiKey: KMLJVJRQAFXKKA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.62
• 重原子数：
  5.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  tetrachloro-l5-phosphane 、 2,2-二氟-4-戊烯酸 反应 0.33h， 生成 2.2-difluoro-4-pentenoic acid
  参考文献：
  名称：

  Process for the preparation of 2,2-difluoropent-4-enoic acids and acid

  摘要：

  在锌的存在下，加热联烯基溴或氯二氟乙酸酯与单氯硅烷反应，可得到α,α-二氟-γ,δ-戊烯酸的硅酯。通过水解可以得到自由酸，从而可以用传统方法制备酸衍生物。戊烯酸和戊烯酸衍生物适用于制备聚合物和共聚物，从中可以获得具有催化性质的金属有机聚合物和共聚物。

  公开号：

  US04892962A1
• 作为产物：
  描述：

  三氯化磷 以 二氯甲烷 为溶剂， 生成 tetrachloro-l5-phosphane
  参考文献：
  名称：

  三氯化磷和二甲基硫醚混合物中的自由基阳离子。结合ESR和量子化学研究

  摘要：

  Exposure of phosphorus trichloride (Cl3P) and dimethyl sulfide (Me2S) dissolved in halocarbons (CFCl3, CF3CCl3, CF2ClCFCl2, and CH2Cl2) to X rays at 77 K results in the corresponding parent cations and several cation-substrate adducts. The radicals are detected and identified by ESR spectroscopy. In dilute solution exclusive formation of the parent Cl3P.+ and Me2S.+ radical cations is observed. In CFCl3, Me2S.+ exhibits superhyperfine interactions due to chlorine and fluorine nuclei of the matrix molecule(s). At increased concentration, or on warning the sample, the parent radical cations readily react with dissolved Cl3P or Me2S molecules to form homodimeric Cl3P-PCl3+ and Me2S-SMe2+ and heterodimeric Cl3P-SMe2+ radical cations with a two-center three-electron sigma(2)sigma*1 bond. The heterodimer is formed in spite of a significant difference between the ionization potentials of the two constituents in reduced form. On further annealing, the Cl3P-PCl3+ cation rearranges to the well-known trigonal-bipyramidal Cl4P. radical and an as yet unidentified configuration. Candidates for the latter are proposed. In concentrated frozen solutions an unexpected reaction of Me2S-SMe2+ and Cl3P is observed, resulting in the heterotrimer Cl3P(SMe2)2*+ with an octahedral configuration, exhibiting a very large P-31 hyperfine interaction (A(iso) = 5115 MHz). Extensive ab initio calculations at the HF/3-21G+ level, including calculation of isotropic and dipolar electron-nuclear hyperfine interactions, confirm the assignments and provide detailed insight into the molecular geometry, electronic configuration, and stability of the radical products.

  DOI：

  10.1021/j100181a020

文献信息

• Reactions of some phosphorus(III) halides with strongly acidic solvents
  作者：Keith B. Dillon、Martin P. Nisbet、Thomas C. Waddington

  DOI：10.1039/dt9790000883

  日期：——

  The reactions of PX3(X = Cl, Br, or I) with the strongly acidic solvents 100% H2SO4, 25 and 65 oleum, HSClO3 and HSFO3, have been investigated by means of 31P n.m.r. spectroscopy. The usual initial reaction is oxidation to [PX3(OH)]+, although HSClO3 also forms [PX3Cl]+. The reduction in acid strength which necessarily accompanies the redox reaction promotes solvolysis of P–X bonds, and halogen exchange

  PX的反应3（X =氯，溴，或I）用强酸性溶剂100％H 2 SO 4，25和65的发烟硫酸，HSClO 3和HSFO 3，已经通过的方法，研究31 P NMR光谱。通常的初始反应是氧化为[PX 3（OH）] +，尽管HSClO 3也形成[PX 3 Cl] +。氧化还原反应必不可少的酸强度的下降会促进P-X键的溶剂分解，并促进HSClO 3和HSFO 3中的卤素交换。由PBr形成[PBr 4 ] +在几种溶剂中也观察到3。在溶液中发现了一些有趣的新物种，尤其是含有P–I键的磷（ V）阳离子，但在25个发烟硫酸中却未发现。在65发烟硫酸中可能发生涉及消除HBr或HI的缩合反应。提出了观察到的各种反应的可能机理。
• Unstable intermediates. Part CLX. An electron spin resonance study of PCl₄, PCl₅^–, PCl₆^2–, and PCl₆radicals in irradiated phosphorus pentachloride
  作者：Shuddhodan P. Mishra、Martyn C. R. Symons

  DOI：10.1039/dt9760000139

  日期：——

  Exposure of phosphorus pentachloride (PCl4+ PCl6–) to 60Co γ-rays at 77 K gave PCl4 and PCl5– radicals in comparable yields, together with a species thought to be PCl62– in lower yield. The isotropic 31P hyperfine coupling increases in this order (ca. 1 310 G, 1 617 G, and 1 815 G respectively). At 77 K PCl4 has two inequivalent chloride ligands (Aisoca. 35 G and 0 G respectively). The PCl5– species

  五氯化磷的曝光（PCL 4 +的PCl 6 - ），以60个钴γ射线在77K给出的PCl 4和PCL 5 -在可比的产率的基团，连同一个物种认为是的PCl 6 2-中产率较低。各向同性31以该顺序（P超精细耦合增加CA 1 310 G，1 617ģ分别和1 815 G）。在77 K，PCl 4具有两个不等价的氯化物配体（分别为A iso约35 G和0 G）。PCl 5 –该物种表现出较小的，较差的分辨，分裂，被解释为与四个等效的氯配体偶联。被认为是PCl 6 2的物种也表现出从多个氯化物配体的多重分裂，但是特征的重叠使得不可能进行准确的评估。
• Reactions of some phosphorus(III) halides with halogens in strongly acidic solvents
  作者：Keith B. Dillon、Martin P. Nisbet、Thomas C. Waddington

  DOI：10.1039/dt9790001591

  日期：——

  The reactions of some phosphorus(III) halides with halogens in the strongly acidic solvents 25 oleum, HSFO3, and 100% H2SO4 have been investigated by means of 31P n.m.r. spectroscopy. The compound PCl3 and Br2, and PBr3and Cl2, react to give complex mixtures of products containing tetrahalogenophosphonium ions [PBr4–nCln]+, together with solvolysed species [PBr3–nCln(OH)]+(25 oleum) or PF3O(HSFO3)

  已通过31 P nmr光谱研究了一些磷（III）卤化物与卤素在强酸性溶剂25发烟硫酸，HSFO 3和100％H 2 SO 4中的反应。化合物PCl 3和Br 2以及PBr 3和Cl 2反应生成复杂的混合物，该混合物包含四卤代phosph离子[PBr 4– n Cl n ] +和溶剂分解的物质[PBr 3– n Cl n（OH）]。+（25发烟硫酸）或PF 3 O（HSFO3）。尽管已从中鉴定出部分溶剂化的物质[ Pn n X 3– n（OH）] +（X = Cl或Br），但没有发现源自PI 3的卤代磷离子[PX n Y 4– n ] +的证据。解决方案。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: P: MVol.C, 196, page 449 - 451
  作者：

  DOI：——

  日期：——
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: P: MVol.C, 232, page 531 - 533
  作者：

  DOI：——

  日期：——