五苯基銻
| 五苯基銻 | |
|---|---|
| |
| IUPAC名 Pentaphenyl-λ5-stibane | |
| 識別 | |
| CAS號 | 2170-05-0 
|
| PubChem | 11813170 |
| ChemSpider | 9987829 |
| SMILES |
|
| 性質 | |
| 化學式 | C30H25Sb |
| 摩爾質量 | 507.28 g·mol−1 |
| 外觀 | 無色固體 |
| 熔點 | 169-170°C |
| 相關物質 | |
| 其他陽離子 | PPh5 AsPh5 BiPh5 |
| 相關化學品 | 五甲基銻 五乙基銻 |
| 若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。 | |
五苯基銻是一種有機銻化合物，由五個苯基和一個銻原子組成，化學式 Sb(C6H5)5，簡稱SbPh5。
性質
五苯基銻是無色固體，熔點 169-170°C。[1]
固體五苯基銻分子是四方錐型結構的。它和溶劑（例如環己烷和四氫呋喃，但不包括乙醚）形成的配合物是三角雙錐結構的。[2]五苯基銻溶液的分子結構也是三角雙錐。[2]然而在NMR的溶液中，五個苯基都是一樣的。這可能是因為分子的形狀不穩定，苯基的方向變化很快導致的。[3]
五苯基銻是三斜晶系的，空間群 P1。它的晶格參數為 a=10.286、b=10.600 和c=13.594 Å，α=79.20°、β=70.43°和γ=119.52°。水平方向的 Sb-C 鍵長為 2.216 Å，垂直方向的 Sb-C 鍵長則為 2.115 Å。[1]
反應
五苯基銻和多種試劑反應，取代一個或多個苯基。它和酸性氫反應會產生副產物苯，而鹵素分子（或它們的合成子）會產生鹵苯：
- Ph5Sb + HOR → PhH + Ph4SbOR
- Ph5Sb + HX → PhH + Ph4SbX
- Ph5Sb + X2 → PhX + Ph4SbX
舉個例子，五苯基銻和二羧酸反應，其中一個苯基被酸性氫取代。這會產生四苯基銻(V)陽離子。[4][5][6][7]
五苯基銻和溴反應，產生溴苯和四苯基溴化銻。它和溴化氫反應，生成四苯基溴化銻和苯。五苯基銻和甲醇的反應會產生四苯基甲氧基銻和三苯基二甲氧基銻。它和四氯化碳反應，產生四苯基氯化銻、苯和氯苯。上面的所有反應似乎都涉及苯基自由基。[8]
製備
參考資料
- ^ 1.0 1.1 1.2 Beauchamp, A. L.; Bennett, Michael J.; Cotton, F. Albert. A reinvestigation of the crystal and molecular structure of pentaphenylantimony. Journal of the American Chemical Society. November 1968, 90 (24): 6675–6680. doi:10.1021/ja01026a020.
- ^ 2.0 2.1 Lindquist-Kleissler, Brent; Weng, Monica; Le Magueres, Pierre; George, Graham N.; Johnstone, Timothy C. Geometry of Pentaphenylantimony in Solution: Support for a Trigonal Bipyramidal Assignment from X-ray Absorption Spectroscopy and Vibrational Spectroscopic Data. Inorganic Chemistry. 2021-06-21, 60 (12): 8566–8574. PMID 34087066. doi:10.1021/acs.inorgchem.1c00496.
- ^ Beattie, I. R.; Livingston, K. M. S.; Ozin, G. A.; Sabine, R. The shape of pentaphenylantimony and pentaphenylarsenic in solution. Journal of the Chemical Society, Dalton Transactions. 1972, (7): 784. doi:10.1039/DT9720000784.
- ^ Sharutin, Vladimir V.; Sharutina, Olga K.; Pakusina, Antonida P.; Belsky, Vitaly K. Reactions of pentaphenylantimony with dicarboxylic acids. Journal of Organometallic Chemistry. May 1997,. 536-537: 87–92. doi:10.1016/S0022-328X(96)06463-7.
- ^ Sharutin, V. V.; Sharutina, O. K.; Gubanova, Yu. O.; El'tsov, O. S. Specific Features of the Reaction between Pentaphenylantimony and Bifunctional Acids: Structures of Bis(tetraphenylantimony) Glutarate, Benzene Solvate of Bis(tetraphenylantimony) 1,4-Cyclohexanedicarboxylate, Dioxane Solvate of Triphenylantimony Hydroxybenzoate, and Triphenylantimony 3-Hydroxybenzoate Adduct with Tetraphenylantimony Tetraphenylstiboxybenzaote and Toluene. Russian Journal of Inorganic Chemistry. September 2019, 64 (9): 1138–1145. S2CID 203852991. doi:10.1134/S0036023619090195.
- ^ Sharutin, Vladimir V.; Sharutina, Olga K.; Gubanova, Yulia O.; Bregadze, Vladimir I.; Glazun, Sergey A. Interaction of pentaphenylantimony with carboranedicarboxylic acid. Journal of Organometallic Chemistry. December 2015, 798: 41–45. doi:10.1016/j.jorganchem.2015.09.002.
- ^ Razuvaev, G.; Sharutin, V. Some reactions of bis(cyclopentadienyl)diferrocenyltitan. "Bulletin of the South Ural State University Series "Chemistry"". 2015, 15 (4): 9–12. doi:10.14529/chem150403
.
- ^ 8.0 8.1 Shen, Kei-Wei; McEwen, William E.; Wolf, Alfred Peter. Photolysis and thermolysis of pentaphenylantimony in benzene. Journal of the American Chemical Society. March 1969, 91 (6): 1283–1288. doi:10.1021/ja01034a003.
擴展閱讀
- Smirnova, N.N.; Letyanina, I.A.; Larina, V.N.; Markin, A.V.; Sharutin, V.V.; Senchurin, V.S. Thermodynamic properties of pentaphenylantimony Ph5Sb over the range from T→0K to 400K. The Journal of Chemical Thermodynamics. January 2009, 41 (1): 46–50. doi:10.1016/j.jct.2008.08.002.
- Brock, C. P.; Ibers, J. A. The role of crystal packing forces in the structure of pentaphenylantimony. Acta Crystallographica Section A. 1976-01-01, 32 (1): 38–42. doi:10.1107/S0567739476000065.