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化学学报
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化学学报 ›› 2009, Vol. 67 ›› Issue (20): 2355-2362. 上一篇    下一篇

研究论文

硅烷基五羰基锰（ＣＯ）５ＳｉＲ３的光化学合成

徐崇福*,a   房俊卓b   薛冰a   周柳怡a   韩峰a   李贞奇a   

  1. (a江苏工业学院化学化工学院 江苏省精细石油化工重点实验室 常州 213164) (b宁夏大学化学化工学院 天燃气转化技术国家重点实验室培育基地 银川 750021)
  • 投稿日期:2009-01-12 修回日期:2009-03-17 发布日期:2009-06-28
  • 通讯作者: 徐崇福 E-mail:xu_chf@163.com

Photochemical Syntheses of Silyl Manganese Pentacarbonyls (CO)5SiR3

Xu, Chongfu*,a    Fang, Junzhuob    Xue, Binga    Zhou, liuyia    Han, Fenga    Li, Zhenqia   

  1. (a Jiangsu Province Key Laboratory of Petrochemical Engineering, College of Chemistry and Chemical Engineering, Jiangsu Polytechnic University, Changzhou 213164) (b State Key Laboratory Breeding Base of Natural Gas Conversion, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021)
  • Received:2009-01-12 Revised:2009-03-17 Published:2009-06-28

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摘要 对甲基卞基五羰基锰(CO)5Mn-p-CH2C6H4CH3（4a）或对甲氧基五羰基锰(CO)5Mn-p-CH2C6H4OCH3（4b）与1-2当量R3SiH的C6H6 或C6D6溶液在5oC光解，经色谱纯化后得到中等或高收率硅烷基五羰基锰(CO)5MnSiR3［SiR3 = SiMe2Ph（１b），SiMePh2（１c），SiPh3（１d），SiHPh2（１e），SiEt3（１f），SiMe2tBu（１g），和SiMe2Et（１h）］。光化学反应后，对二甲苯和对甲基苯甲醚副产物分别定量生成，并伴随少量Mn2(CO)10（<1％-6％）。色谱柱的尺寸和温度（室温至- 65 oC）的选择视初始浓度的分解，色谱柱展开期间1的稳定性（过载），以及1与Mn2(CO)10的分离难易而定。去除Mn2(CO)10后的硅烷基五羰基锰3b-3g为浅黄色油状物或无色晶体（只有3h无法分离得到纯净物）。尽管这些化合物对空气敏感对热却相对稳定。

关键词: 光化学合成, 硅烷基五羰基锰, 变温色谱分离

Abstract Photolysis of paramethyl benzyl manganese pentacarbonyl (CO)5Mn-p-CH2C6H4CH3 (4a)and paramethoxy benzyl manganese pentacarbonyl (CO)5Mn-p-CH2C6H4OCH3(4b) with 1-2 equivalents of R3SiH in C6H6 or C6D6 at 5℃ yields the silyl manganese pentacarbonyls (CO)5MnSiR3 [SiR3 = SiMe2Ph (1b), SiMePh2 (1c), SiPh3 (1d), SiHPh2 (1e), SiEt3 (1f), SiMe2tBu(1g), and SiMe2Et (1h) ] in moderate to high yields after chromatographic purification. Quantitative production of respective byproducts p-xylene and p-methylanisole, along with variable yields of Mn2(CO)10 (<1 % to 6 %) are observed after the photochemical reaction. Conditions for the chromatographic isolation differ for each product. Choice of column size and temperature (room temperature to - 65 ℃) is made according to initial concentration-dependent decomposition (overloading), stability during development and separability of 1 with Mn2(CO)10. Once freed from Mn2(CO)10 1b - 1g were isolated as pale yellow oil or off white crystals (only 3h was not isolated pure). Although very air sensitive these products are otherwise stable thermally.

Key words: photochemical synthesis, silyl manganese pentacarbonyl, variable temperature chromatographic isolation