Tetraselena crown ethers: synthesis and complexation with mercury salts. Crystal structure of a macrocycle and a mercury(II) complex
作者:Ahmed Mazouz、Philippe Meunier、Marek M. Kubicki、Bernard Hanquet、Régine Amardeil、Céline Bornet、Assou Zahidi
DOI:10.1039/a606674g
日期:——
Dipotassium benzene-1,2-diselenolate,
C
6
H
4
(SeK)
2
-1,2 obtained from the
reaction of potassium tert-butoxide with a
(benzene-1,2-diselenolato)zirconocene, was treated with
C
6
H
4
[SeCH
2
(CH
2
OCH
2
)
n
CH
2
X]
2
-1,2
(X = Cl, n = 1 1,
n = 2 2, n = 3
3 or X = Br n = 3
4) leading to tetraselenacrown ethers
C
6
H
4
[SeCH
2
(CH
2
OCH
2
)
n
CH
2
Se]
2
C
6
H
4
(n = 1 6,
n = 2 7 or n = 3
8) in a moderate yield (10–20%). This yield can be
increased by using the ‘caesium effect' from benzene-1,2-diselenol
(18–40%). These macrocyclic compounds are able to complex heavy
metals [especially mercury(II) ions] via their
selenium atoms. The mercury complexes have been characterized by
multinuclear NMR spectroscopy. The molecular structures of the
tetraselenacrown ether 7 and the mercury complex of macrocycle
8 have been established by X-ray diffraction.
用 C 6 H 4 [SeCH 2 (CH 2 OCH 2 ) n CH 2 X] 2 -1 处理叔丁醇钾与(苯-1,2-二硒醇)二茂锆反应得到的苯-1,2-二硒酸二钾 C 6 H 4 (SeK) 2 -1,22 (X = Cl, n = 1 1, n = 2 2, n = 3 3 或 X = Br n = 3 4) 处理,得到四硒冠醚 C 6 H 4 [SeCH 2 (CH 2 OCH 2 ) n CH 2 Se] 2 C 6 H 4 (n = 1 6, n = 2 7 或 n = 3 8),收率为中等(10-20%)。利用苯-1,2-二硒醇的 "铯效应 "可以提高产率(18-40%)。这些大环化合物能够通过其硒原子络合重金属(尤其是汞(II)离子)。这些汞络合物的特征已通过多核核磁共振光谱分析得到。通过 X 射线衍射,确定了四硒冠醚 7 和大环 8 汞络合物的分子结构。