五苯基锑

五苯基锑
IUPAC名
Pentaphenyl-λ5-stibane
识别
CAS号 2170-05-0  checkY
PubChem 11813170
ChemSpider 9987829
SMILES
 
  • C1=CC=C(C=C1)[Sb](C2=CC=CC=C2)(C3=CC=CC=C3)(C4=CC=CC=C4)C5=CC=CC=C5
性质
化学式 C30H25Sb
摩尔质量 507.28 g·mol−1
外观 无色固体
熔点 169-170°C
相关物质
其他阳离子 PPh5
AsPh5
BiPh5
相关化学品 五甲基锑
五乙基锑
若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

五苯基锑是一种有机锑化合物，由五个苯基和一个锑原子组成，化学式 Sb(C6H5)5，简称SbPh5。

性质

五苯基锑是无色固体，熔点 169-170°C。[1]

固体五苯基锑分子是四方锥型结构的。它和溶剂（例如环己烷和四氢呋喃，但不包括乙醚）形成的配合物是三角双锥结构的。[2]五苯基锑溶液的分子结构也是三角双锥。[2]然而在NMR的溶液中，五个苯基都是一样的。这可能是因为分子的形状不稳定，苯基的方向变化很快导致的。[3]

五苯基锑是三斜晶系的，空间群 P1。它的晶格参数为 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 键长为 2.216 Å，垂直方向的 Sb-C 键长则为 2.115 Å。[1]

反应

五苯基锑和多种试剂反应，取代一个或多个苯基。它和酸性氢反应会产生副产物苯，而卤素分子（或它们的合成子）会产生卤苯：

Ph5Sb + HOR → PhH + Ph4SbOR
Ph5Sb + HX → PhH + Ph4SbX
Ph5Sb + X2 → PhX + Ph4SbX

举个例子，五苯基锑和二羧酸反应，其中一个苯基被酸性氢取代。这会产生四苯基锑(V)阳离子。[4][5][6][7]

五苯基锑加热分解成三苯基锑、联苯和对四联苯（英语：p-quaterphenyl）。[8]

五苯基锑和溴反应，产生溴苯和四苯基溴化锑。它和溴化氢反应，生成四苯基溴化锑和苯。五苯基锑和甲醇的反应会产生四苯基甲氧基锑和三苯基二甲氧基锑。它和四氯化碳反应，产生四苯基氯化锑、苯和氯苯。上面的所有反应似乎都涉及苯基自由基。[8]

制备

五苯基锑可以由二氯三苯基锑和苯基锂反应而成。[1]

参考资料

  1. ^ 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. ^ 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. 
  3. ^ 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. 
  4. ^ 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. 
  5. ^ 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. 
  6. ^ 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. 
  7. ^ 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 可免费查阅. 
  8. ^ 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. 

扩展阅读

  • 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.