四溴化钛

四溴化钛
IUPAC名
Titanium(IV) bromide
英文名 Titanium tetrabromide
别名 溴化钛、溴化钛(IV)
识别
CAS号 7789-68-6  checkY
PubChem 123263
SMILES
 
  • [Ti](Br)(Br)(Br)Br
InChI
 
  • 1S/4BrH.Ti/h4*1H;/q;;;;+4/p-4
EINECS 232-185-0
性质
化学式 TiBr4
摩尔质量 367.483 g·mol⁻¹
外观 琥珀色固体[1]
密度 3.25 g/cm3[2]
熔点 39.5 °C(312.6 K)[3]
沸点 233.4 °C(506.5 K)[4]
溶解性 水解[1]
溶解性 易溶于醇[1]
可溶于醚[1]
可溶于浓盐酸[1]
结构
晶体结构 立方晶系, Pa3, Z = 8
配位几何 四面体
偶极矩 0 D
危险性
警示术语 R:14-34
安全术语 S:26-36/37/39-45
主要危害 腐蚀性
NFPA 704
0
3
1
 
闪点 不可燃
相关物质
其他阴离子 四氯化钛
四氟化钛
四碘化钛
相关化学品 三溴化钛
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

四溴化钛的化学式是TiBr4,其性质介于四碘化钛四氯化钛之间。这类4价钛的四配物有些关键的通性,如路易士酸性较高,且易溶于非极性有机溶剂。TiBr4为抗磁性物质,中心原子的外层电子组态为d0[5]

制备

四溴化钛可以由四氯化钛溴化氢反应而成。[1]

四溴化钛也可以由以下反应产生:[1]

非常纯的四溴化钛可以由二溴化铅和钛反应而成。[1]

性质

四溴化钛是一种琥珀黄色晶体。它极易潮解,会水解成二氧化钛和氢溴酸。刚结晶的四溴化钛是四碘化锡结构的,空间群 Pa3 (No. 205),晶格参数 a = 1130.0 pm。放置很久的四溴化钛会转变成四溴化锡结构,空间群 P21/c (No. 14),晶格参数 a = 1017 pm、b = 709 pm、c = 1041 pm 和β = 101.97°。[1][6]

反应

四溴化钛会形成加合物,如 TiBr4(THF)2 和 [TiBr5][7] 它和2-甲基吡啶 (2-Mepy)配合,形成五配位的 TiBr4(2-MePy)。这种分子是三角双锥构型的,吡啶环在水平方向。[8]

TiBr4有机合成中可用作路易斯酸催化剂[9]

四溴化钛和四氯化钛混合,会形成各种通式 TiBr4−xClx (x = 0-4)的化合物。它的机理不明。[10]

参考文献

  1. ^ 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 Georg Brauer (Hrsg.), unter Mitarbeit von Marianne Baudler u. a.: Handbuch der Präparativen Anorganischen Chemie. 3., umgearbeitete Auflage. Band II, Ferdinand Enke, Stuttgart 1978, ISBN 3-432-87813-3, S. 1348ff.
  2. ^ 来源:Sigma-Aldrich Co., product no. {{{id}}} .
  3. ^ Fritsch, Pierre. Magnetic rotatory power of TiBr4. Compt. rend., 1943. 217: 447.
  4. ^ Rolf B. Johannesen, Charles L. Gordon, Karl H. Gayer, Lawrence Balash. S. Y. Tyree , 编. Titanium(IV) Bromide. Hoboken, NJ, USA: John Wiley & Sons, Inc. 2007-01-05: 46–50 [2021-01-12]. ISBN 9780470132401. doi:10.1002/9780470132401.ch14. 
  5. ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  6. ^ Jean D'Ans, Ellen Lax, [《四溴化钛》在Google Books的內容。 Taschenbuch für Chemiker und Physiker], Springer DE. 1997: pp. 766, (德文) 
  7. ^ Colin S. Creaser & J. Alan Creighton. Pentachloro- and pentabromo-titanate(IV) ions. J. Chem. Soc., Dalton Trans. 1975, (14): 1402–1405. doi:10.1039/DT9750001402. 
  8. ^ Hensen, K.; Lemke, A.; Bolte, M. Tetrabromo(2-methylpyridine-N)-titanate(IV). Acta Crystallographica. 2000, C56 (12): e565–e566. doi:10.1107/S0108270100015407. 
  9. ^ B. Patterson, S. Marumoto & S. D. Rychnovsky. Titanium(IV)-Promoted Mukaiyama Aldol-Prins Cyclizations. Org. Lett. 2003, 5 (17): 3163–3166. PMID 12917007. doi:10.1021/ol035303n. 
  10. ^ S. P. Webb & M. S. Gordon. Intermolecular Self-Interactions of the Titanium Tetrahalides TiX4 (X = F, Cl, Br). J. Am. Chem. Soc. 1999, 121 (11): 2552–2560 [2021-07-17]. doi:10.1021/ja983339i. (原始内容存档于2021-05-15). 

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