碘化𬭸
化合物
碘化鏻是一種化合物,化學式為PH
4I。它含有未取代的鏻陽離子(PH+
4)。碘化鏻通常用作磷化氫的儲存劑[1]和用磷取代有機分子的試劑。[2]
碘化𬭸 | |
---|---|
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IUPAC名 Phosphanium iodide | |
别名 | 碘化膦 |
识别 | |
CAS号 | 12125-09-6 |
PubChem | 166618 |
ChemSpider | 145802 |
SMILES |
|
EINECS | 235-189-0 |
性质 | |
化学式 | PH4I |
摩尔质量 | 161.910 g·mol⁻¹ |
沸点 | 62 °C(335 K) |
溶解性(水) | 分解 |
结构 | |
晶体结构 | 四方 (P4/nmm) |
晶格常数 | a = 6.34 Å, c = 4.62 Å |
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。 |
製備
碘化鏻是由四碘化二磷在80 °C下用白磷和水使其昇華製備:[3][4]
- 10 P
2I
4 + 13 P
4 + 128 H
2O → 40 PH
4I + 32 H
3PO
4
- PH
3 + HI ⇌ PH
4I
向白磷和三碘化磷的混合物中加水得到:
- 3P
4 + 2PI
3 + 24H
2O → 6PH
4I + 8H
3PO
4
性質
結構
其晶體結構具有四方空間群P4/nmm,是NH4Cl晶體結構的扭曲版本,晶胞的尺寸約為634×634×462pm。[5]體系中的氫鍵導致PH+
4陽離子有方向性,使氫原子指向I−
陰離子。[6]
化學性質
在62°C和大氣壓下,碘化鏻會昇華並可逆分解為磷化氫和碘化氫。[7]在空氣中緩慢氧化生成碘和五氧化二磷。它具有吸濕性[3],會水解成磷化氫和碘化氫:[8]
- PH
4I ⇌ PH
3 + HI
通過將水溶液與氫氧化鉀混合,可以從碘化鏻中脫除磷化氫氣體:[9]
- PH
4I + KOH → PH
3 + KI + H
2O
- 2PH
4I + 5I
2 → P
2I
4 + 8HI[3]
碘化鏻是有機化學中一種強有力的取代試劑,例如它可以通過取代將吡啶鎓轉化為膦。[2]1951年,Glenn Halstead Brown發現碘化鏻與乙酰氯反應生成未知的膦衍生物,可能是CH
3C(=PH)PH
2 · HI。[3]
參考資料
- ^ Morrow, B. A.; McFarlane, Richard A. Trimethylgallium adsorbed on silica and its reaction with phosphine, arsine, and hydrogen chloride: an infrared and Raman study. The Journal of Physical Chemistry. July 1986, 90 (14): 3192–3197. ISSN 0022-3654. doi:10.1021/j100405a029.
- ^ 2.0 2.1 Mei, Yanbo. Complexes, Heterocycles, and Depolymerizable Polymers. Made from Building Blocks with Low-coordinated Phosphorus (学位论文). ETH Zurich: 18. 2020 [6 October 2020]. doi:10.3929/ethz-b-000431853. hdl:20.500.11850/431853. (原始内容存档于2020-10-15).
- ^ 3.0 3.1 3.2 3.3 Brown, Glenn Halstead. Reactions of phosphine and phosphonium iodide (学位论文). Iowa State College. 1951 [5 Oct 2020]. (原始内容存档于2020-10-09).
- ^ Work, J. B.; Mattern, J. A.; Antonucci, R. Phosphonium Iodide. Inorganic Syntheses. 5 January 2007: 141–144. doi:10.1002/9780470132333.ch41.
- ^ Dickinson, Roscoe G. The Crystal Structure of Phosphonium Iodide. Journal of the American Chemical Society. July 1922, 44 (7): 1489–1497 [2023-05-01]. doi:10.1021/ja01428a015. (原始内容存档于2023-05-04).
- ^ Sequeira, A.; Hamilton, Walter C. Hydrogen Bonding in Phosphonium Iodide: A Neutron-Diffraction Study. The Journal of Chemical Physics. September 1967, 47 (5): 1818–1822. Bibcode:1967JChPh..47.1818S. doi:10.1063/1.1712171.
- ^ Smith, Alexander.; Calvert, Robert Peyton. The Dissociation Pressures of Ammonium- and Tetramethylammonium Halides and of Phosphonium Iodide and Phosphorus Pentachloride. Journal of the American Chemical Society. July 1914, 36 (7): 1363–1382 [6 October 2020]. doi:10.1021/ja02184a003.
- ^ Levchuk, Ievgen. Design and optimization of luminescent semiconductor nanocrystals for optoelectronic applications (PDF) (学位论文). University of Erlangen–Nuremberg: 140. 2017 [6 Oct 2020]. (原始内容存档 (PDF)于2023-05-01).
- ^ Osadchenko, Ivan M; Tomilov, Andrei P. Phosphorus Hydrides. Russian Chemical Reviews. 30 June 1969, 38 (6): 495–504. Bibcode:1969RuCRv..38..495O. S2CID 250872306. doi:10.1070/RC1969v038n06ABEH001756.
延伸閱讀
- Химическая энциклопедия / Редкол.: Зефиров Н.С. и др.. — М.: Большая Российская энциклопедия, 1998. — Т. 5. — 783 с. — ISBN 5-85270-310-9.
- Справочник химика / Редкол.: Никольский Б.П. и др.. — 2-е изд., испр. — М.-Л.: Химия, 1966. — Т. 1. — 1072 с.
- Справочник химика / Редкол.: Никольский Б.П. и др.. — 3-е изд., испр.. — Л.: Химия, 1971. — Т. 2. — 1168 с.
- Лидин Р.А. и др. Химические свойства неорганических веществ: Учеб. пособие для вузов. — 3-е изд., испр.. — М.: Химия, 2000. — 480 с. — ISBN 5-7245-1163-0.