五苯基磷

五苯基磷
	IUPAC名; pentakis-phenyl-λ5-phosphane
識別
CAS號	2588-88-7
PubChem	2785233
ChemSpider	2065130
SMILES	C1=CC=C(C=C1)P(C2=CC=CC=C2)(C3=CC=CC=C3)(C4=CC=CC=C4)C5=CC=CC=C5;
性質
化學式	C30H25P
摩爾質量	416.49 g·mol−1
外觀	無色
密度	1.22
相關物質
其他陽離子	五苯基砷; 五苯基銻; 五苯基鉍
相關化學品	三苯基磷
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

五苯基磷是一種正膦，由五個苯基和一個中心磷原子組成，它的氧化態為+5。五苯基磷的化學式為P(C₆H₅)₅，簡稱Ph₅P，其中的Ph是苯基。它是由格奧爾格·維蒂希在1949年發現和報告的。^[2]

製備

五苯基磷可以由苯基鋰和四苯基溴化鏻^[3]或四苯基碘化鏻反應而成。^[2]

性質

五苯基磷的分子結構為三角雙錐。它是單斜晶系的，晶格參數a=10.03、b=17.22、c=14.17 Å和β=112.0°，空間群Cc。^[4]五苯基磷也可以被溶劑溶劑化。

它和四氫呋喃產生的晶體是三斜晶系的，空間群P1，晶格參數a=10.095、b=10.252、c=12.725 Å，α=71.21、β=76.98、γ=87.12。^[5]它也可以和環己烷^[6]或苯形成溶劑晶體。^[7]

反應

五苯基磷加熱分解成聯苯和三苯基膦。^[2]

五苯基磷和酸性氫反應，產生四苯基鏻陽離子和苯。^[2]舉個例子，五苯基磷和羧酸、磺酸反應，產生對應的四苯基鏻羧酸鹽或磺酸鹽。^[8]

五苯基磷會把苯基轉移給有機汞化合物和有機錫化合物。舉個例子，它和苯基氯化汞反應，產生二苯基汞和四苯基氯化鏻。它和三丁基氯化錫的反應會產生三丁基苯基錫。不過，五苯基磷和二氟三苯基鉍、二氯三苯基鉍或二溴三苯基鉍的反應只會產生三苯基鉍和氟苯、氯苯或溴苯。這可能是因為四苯基鹵化鉍（Ph₄BiF、Ph₄BiCl、Ph₄BiBr）會自發分解導致的。^[9]

參考資料

^ Freeman, B.H.; Lloyd, D.; Singer, M.I.C. Tetraphenylcyclopentadienylides. Tetrahedron. January 1972, 28 (2): 343–352. doi:10.1016/0040-4020(72)80141-8.
^ ^2.0 ^2.1 ^2.2 ^2.3 Wittig, Georg; Rieber, Martin. Über die Metallierbarkeit von quaternären Ammonium- und Phosphonium-Salzen. Justus Liebigs Annalen der Chemie. 1949-05-10, 562 (3): 177–186. doi:10.1002/jlac.19495620303.
^ Seyferth, Dietmar.; Fogel, Joseph S.; Heeren, James K. The Reaction of Vinyllithium with Tetraphenylphosphonium Bromide and the Formation of Phosphinemethylenes by RLi Addition to Vinylphosphonium Halides. Journal of the American Chemical Society. January 1964, 86 (2): 307–308. doi:10.1021/ja01056a059.
^ Wheatley, P. J. 408. The crystal and molecular structure of pentaphenylphosphorus. Journal of the Chemical Society (Resumed). 1964: 2206. doi:10.1039/JR9640002206.
^ Müller, Gerhard; Bildmann, Ulrich Jürgen. Crystal and Molecular Structure of P(C 6 H 5 ) 5 · 0.5 THF. Zeitschrift für Naturforschung B. 2004-12-01, 59 (11–12): 1411–1414. S2CID 99733089. doi:10.1515/znb-2004-11-1207.
^ Brock, C. P. Lattice energy calculations for (C 6 H 5 ) 5 M 0.5C 6 H 12 , M = P, As and Sb: towards an understanding of crystal packing in the pentaphenyl group V compounds. Acta Crystallographica Section A. 1977-11-01, 33 (6): 898–902. Bibcode:1977AcCrA..33..898B. doi:10.1107/S0567739477002204.
^ Губанова, Юлия Олеговна; Шарутина, Ольга Константиновна. Синтез и строение карбоксилатов тетрафенилфосфония [Ph 4 P][OC(O)C 6 H 3 (OH) 2 -2,6], [Ph 4 P][OC(O)CH 2 CH 2 C(O)OH] [Synthesis and Structure of Tetraphenylphosphonium Carboxylates [Ph4P][OC(O)C6H3 (OH) 2-2,6], [Ph4P][OC(O)CH2CH2C(O)OH]]. Химия. 2020-08-16, 12 (3): 79–87 [2021-07-27]. （原始內容存檔於2020-12-10）（俄語）.
^ Shaturin, V. V.; Senchurin, V. S.; Shaturina, O. K.; Boyarkina, E. A. Tetraphenylphosphonium carboxylates and sulfonates. Synthesis and structure. Russian Journal of General Chemistry. January 2009, 79 (1): 78–87. S2CID 96900890. doi:10.1134/S1070363209010125.
^ Sharutin, V. V.; Sharutina, O. K.; Senchurin, V. S.; Egorova, I. V.; Ivanenko, T. K.; Petrov, B. I. [No title found]. Russian Journal of General Chemistry. 2003, 73 (2): 202–203. S2CID 91420871. doi:10.1023/A:1024731719528.

擴展閱讀

Zykova, A.R. РЕАКЦИЯ ПЕНТАФЕНИЛФОСФОРА С ГЕКСАХЛОРОПЛАТИНОВОЙ КИСЛОТОЙ [Reaction of Pentaphenylphosphorus with Hexachloroplatinic Acid]. Bulletin of the South Ural State University Series "Chemistry". 2021, 13 (1): 31–38. doi:10.14529/chem210103  （俄語）.
Hoffmann, Roald; Howell, James M.; Muetterties, Earl L. Molecular orbital theory of pentacoordinate phosphorus (PDF). Journal of the American Chemical Society. May 1972, 94 (9): 3047–3058 [2021-07-27]. doi:10.1021/ja00764a028. （原始內容 (PDF)存檔於2020-01-10）.

[1] Freeman, B.H.; Lloyd, D.; Singer, M.I.C. Tetraphenylcyclopentadienylides. Tetrahedron. January 1972, 28 (2): 343–352. doi:10.1016/0040-4020(72)80141-8.

[wittig-2] 2.0 ^2.1 ^2.2 ^2.3 Wittig, Georg; Rieber, Martin. Über die Metallierbarkeit von quaternären Ammonium- und Phosphonium-Salzen. Justus Liebigs Annalen der Chemie. 1949-05-10, 562 (3): 177–186. doi:10.1002/jlac.19495620303.

[3] Seyferth, Dietmar.; Fogel, Joseph S.; Heeren, James K. The Reaction of Vinyllithium with Tetraphenylphosphonium Bromide and the Formation of Phosphinemethylenes by RLi Addition to Vinylphosphonium Halides. Journal of the American Chemical Society. January 1964, 86 (2): 307–308. doi:10.1021/ja01056a059.

[4] Wheatley, P. J. 408. The crystal and molecular structure of pentaphenylphosphorus. Journal of the Chemical Society (Resumed). 1964: 2206. doi:10.1039/JR9640002206.

[5] Müller, Gerhard; Bildmann, Ulrich Jürgen. Crystal and Molecular Structure of P(C 6 H 5 ) 5 · 0.5 THF. Zeitschrift für Naturforschung B. 2004-12-01, 59 (11–12): 1411–1414. S2CID 99733089. doi:10.1515/znb-2004-11-1207.

[6] Brock, C. P. Lattice energy calculations for (C 6 H 5 ) 5 M 0.5C 6 H 12 , M = P, As and Sb: towards an understanding of crystal packing in the pentaphenyl group V compounds. Acta Crystallographica Section A. 1977-11-01, 33 (6): 898–902. Bibcode:1977AcCrA..33..898B. doi:10.1107/S0567739477002204.

[7] Губанова, Юлия Олеговна; Шарутина, Ольга Константиновна. Синтез и строение карбоксилатов тетрафенилфосфония [Ph 4 P][OC(O)C 6 H 3 (OH) 2 -2,6], [Ph 4 P][OC(O)CH 2 CH 2 C(O)OH] [Synthesis and Structure of Tetraphenylphosphonium Carboxylates [Ph4P][OC(O)C6H3 (OH) 2-2,6], [Ph4P][OC(O)CH2CH2C(O)OH]]. Химия. 2020-08-16, 12 (3): 79–87 [2021-07-27]. （原始內容存檔於2020-12-10）（俄語）.

[8] Shaturin, V. V.; Senchurin, V. S.; Shaturina, O. K.; Boyarkina, E. A. Tetraphenylphosphonium carboxylates and sulfonates. Synthesis and structure. Russian Journal of General Chemistry. January 2009, 79 (1): 78–87. S2CID 96900890. doi:10.1134/S1070363209010125.

[9] Sharutin, V. V.; Sharutina, O. K.; Senchurin, V. S.; Egorova, I. V.; Ivanenko, T. K.; Petrov, B. I. [No title found]. Russian Journal of General Chemistry. 2003, 73 (2): 202–203. S2CID 91420871. doi:10.1023/A:1024731719528.

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