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有机铊化学

有机铊化学是研究含-键化合物的化学分支。由于它在自然界含量稀少、分布分散且毒性特别大,故没有同族的研究的广泛而深入。在有铊化合物中,铊可以以+1或+3氧化态的形式出现。

铊(III)有机化合物

三烃基铊和同族的三烃基铟不同,因TlX3不稳定而不由三卤化铊直接合成,需要利用二烃基卤化铊:[1]

Ph2TlCl + PhMgBr —THF→ Ph3Tl + MgBrCl

甲基锂碘化亚铊碘甲烷的反应,可以用来制备三甲基铊[2]

2 CH3Li + CH3I + TlI → (CH3)3Tl + 2 LiI

该反应的机理尚有争议。

三烃基铊可以被氢卤酸或羧酸的水溶液分解:

R3Tl + HA —H2O→ R2TlA + RH (A=Cl, Br, I, CH3COO, CF3COO等)

三乙酸铊可以直接和芳烃反应,反应通过亲电取代历程进行:

Tl(CH3COO)3 + ArH → ArTl(CH3COO)2 + CH3COOH

三(三氟乙酸)铊亦可完成此反应。[3]

铊(I)有机化合物

一价的烃基铊通常不稳定,容易发生歧化反应:

3 CH3Tl → (CH3)3Tl + 2 Tl

环戊二烯基铊(C5H5Tl)却相当稳定,它可以在水溶液中制备出来:

2 C5H6 + Tl2SO4 + 2 NaOH → 2 C5H5Tl↓ + Na2SO4 + 2 H2O

C5H5Tl易与卤化物或卤代烃反应,形成其它环戊二烯化合物。环戊二烯基铊具有较高的稳定性,但含有取代基的环戊二烯基铊的稳定性却较差。[4]

参考资料

  1. ^ 宋礼成,王佰全. 金属有机化学原理及应用. 高等教育出版社, 2012.10. pp 149-161. 5.3 镓、铟、铊有机化合物
  2. ^ Gilman H, Jones R G. J Am Chem Soc, 1999, 121: 3228-3229
  3. ^ McKillop A, Fowler J S, Zelesko M J, et al. Tetrahedron Lett, 1969, 10: 2423-2426
  4. ^ 丘昌隆. 环戊二烯基铊(I)的化学. 化学试剂, 1986, 8(6): 3560360
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有机铊化学
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