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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (08): 999-1006. 上一篇    下一篇

研究论文

(CO)5MnSiR3与R 3SiH的光化学硅烷基交换反应研究

徐崇福*,1，房俊卓2，薛冰1，陈颖1   

  1. (1常州大学石油化工学院 江苏省精细石油化工重点实验室 常州 213164)
    (2宁夏大学化学化工学院 天然气转化技术国家重点实验室培育基地 银川 750021)
  • 投稿日期:2010-01-20 修回日期:2010-05-31 发布日期:2010-12-31
  • 通讯作者: 徐崇福 E-mail:xu_chf@163.com
  • 基金资助:

    铂-锰双金属化合物的合成及其在催化中的应用

Study on The Photochemical Silyl Exchange Reactions of (CO)5MnSiR3 With R 3SiH

Xu Chongfu*,1 Fang Junzhuo2 Xue Bing1 Chen Ying1   

  1. (1 Jiangsu Province Key Laboratory of Petrochemical Engineering, College of Petroleum Chemical Engineering, Changzhou University, Changzhou 213164)
    (2 State Key Laboratory Breeding Base of Natural Gas Conversion, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021)
  • Received:2010-01-20 Revised:2010-05-31 Published:2010-12-31
  • Contact: Chong-Fu Xu E-mail:xu_chf@163.com

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五羰基锰硅烷基配合物(CO)5MnSiR3 (3) [SiR3＝SiMe2Ph (3b), SiMePh2 (3c), SiPh3 (3d), SiHPh2 (3e), SiEt3 (3f)和SiMe2Et (3h)]与不同氢硅烷R 3SiH在5 ℃光解1 h, 这两个物种间的硅烷基交换达到平衡. 适中的产物与反应物自由能变化间隔使得这些反应实质上可逆. 光催化经由不饱和物种(CO)4MnSiR3 (1)和过渡中间体(CO)4MnH(SiR3)(SiR 3) (4)进行. 物种3作为通过光活化前催化剂的可行性得到确认. 受电子效应和位阻效应的影响, 含有体积较大且推电子基团(如乙基)的硅烷基更容易被含有体积较小且吸纳电子基团(如负氢)的硅烷基从五羰基锰硅烷基配合物中置换出来.

关键词: 光化学, 五羰基锰硅烷基配合物, 硅烷基交换

Silyl manganese pentacarbonyls (CO)5MnSiR3 [SiR3＝SiMe2Ph (3b), SiMePh2 (3c), SiPh3 (3d), SiHPh2 (3e), SiEt3 (3f), and SiMe2Et (3h)] were photolyzed with different hydrosilanes R 3SiH at 5 ℃ for 1 h, and the equilibrium of the silyl exchange between the two species was established. Moderate free energy gap between the products and reactants makes these reactions essentially reversible. The photocatalysis was preceded via an unsaturated species (CO)4MnSiR3 (1), and a transitional intermediate (CO)4MnH(SiR3)- (SiR 3) (4). Feasibility of species 3 as a precatalyst activated via photolysis was confirmed. Due to both electronic and steric factors, the silyls bearing bulkier and more electrons repelling groups (like ethyl) were more readily to be replaced by that bearing smaller and electron accommodating groups (like hydride) from silyl manganese pentacarbonyls.

Key words: photochemistry, silyl manganese pentacarbonyls, silyl exchange