碘化鏻 是一種化合物,化學式為PH 4 I 。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]
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 2 I 4 + 13 P 4 + 128 H 2 O → 40 PH 4 I + 32 H 3 PO 4
由碘化氢 和磷化氫 直接化合:
PH 3 + HI ⇌ PH 4 I
向白磷和三碘化磷 的混合物中加水得到:
3P 4 + 2PI 3 + 24H 2 O → 6PH 4 I + 8H 3 PO 4
性質
結構
其晶體結構具有四方 空間群P4/nmm,是NH4 Cl 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 4 I ⇌ 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 4 I + KOH → PH 3 + KI + H 2 O
在非極性溶液中與碘 和溴 反應生成對應鹵化磷:
2PH 4 I + 5I 2 → P 2 I 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 3 C(=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 .
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