化学学报 ›› 2008, Vol. 66 ›› Issue (10): 1239-1244. 上一篇    下一篇

研究论文

五羰基锰烷基化合物的合成及光化学反应研究

徐崇福   

  1. 江苏工业学院
  • 投稿日期:2007-06-18 修回日期:1900-01-01 发布日期:2008-05-28
  • 通讯作者: 徐崇福

Synthesis and Photochemical Studies of Alkyl Manganese Pentacarbonyls

Xu Chong-Fu   

  • Received:2007-06-18 Revised:1900-01-01 Published:2008-05-28
  • Contact: Xu Chong-Fu

用五羰基锰钾盐和相应的卤代物在乙醚中的金属化反应合成了五羰基锰烷基合物 (CO)5MnR(R = CH3,p-CH2C6H4CH3, p-CH2C6H4OCH3 ),产率达到72-93%,将这些化合物与1-2当量(CH3)2(C6H5)SiH和(CH3)(C6H5)2SiH的C6D6溶液在5℃光解,分别得到五羰基锰硅烷基化合物(CO)5MnSi(C6H5)(CH3)2和(CO)5MnSi(C6H5)2(CH3)(产率达到70-88%)。在光化学反应中,还观察到相应甲烷,对二甲苯,和对甲基苯甲醚的定量生成,以及少量的Mn2(CO)10(<2%-4%),(CO)4MnH(SiR3)2(<9%)副产物。

Alkyl manganese pentacarbonyl compounds (CO)5MnR (R = CH3, p-CH2C6H4CH3, p-CH2C6H4OCH3) were synthesized by metalation of manganese pentacarbony potassium salt with corresponding alkyl halides in ether. Photolysis of these with 1-2 equivalent of (CH3)2(C6H5)SiH or (CH3)(C6H5)2SiH in C6D6 solution at 5℃ produces silyl manganese pentacarbonyl compounds (CO)5MnSi(C6H5)(CH3)2 and (CO)5MnSi(C6H5)2(CH3) respectively (yield 70-88%). Quantative generation of corresponding methane, p-xylene, p-methyl anisole was also observed along with minor byproducts Mn2(CO)10 (<4%), (CO)4MnH(SiMe2Ph) (<9%).