五羰基乙酰基锰的深度氢硅烷化  

Extensive Hydrosilation of Acetyl Manganese Pentacarbonyl

作　　者：王颖[1,2] 薛冰[1] 李艺林[1] 李司楠 徐崇福[1,2] 

机构地区：[1]常州大学石油化工学院,常州213164 [2]江苏省绿色催化材料与技术重点实验室,常州213164

出　　处：《无机化学学报》2015年第7期1393-1401,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21376032)资助项目

摘　　要：采用两步法合成(CO)5MnCOCH3(1),然后对1与Me2PhSiH的深度氢硅烷化反应做9 h的1H NMR连续监控,通过将反应物和衍生物的特征峰与内标物C6H5(CH2)2C6H5的特征峰对照直接积分定量,得到适时含量(mmol)随反应时间改变(h)的变化规律。期间共得到了9种中间体或最终产物,通过核磁波谱对比,确定了这些化合物的分子结构。除了对其中6种化合物的特征峰积分直接定量外,对另外3个化合物采用化学计量结合特征峰积分间接定量,并对其反应机理做出了合理的解释。最后提出了深度氢硅烷化的多步反应与双通道机理,并且对反应原料1和Me2PhSiH中Mn和Si进行了全程跟踪,结果发现,在9 h时,Mn总含量高达90.7%,而Si总含量高达91.4%。monitored （CO）sMnCOCH3 （1） was synthesized in two steps. A solution 1 with Me2PhSiH in C6D6 was continuously by 1H NMR spectroscopy for 9 h and reaction profile was established using timely contents （mmol） obtained by directly integrating chemical labels of the reactants and derivatives against that of the internal standard CrH5（CH2）2C6H5. 9 intermediates and final products emerged in the extensive hydrosilation were prepared and the molecular structures of the derivations generated in the reaction process were positively confirmed by comparison of their NMR spectra with that of real substances. All besides the 6 species that were quantified by direct integration of their chemical labels the other 3 were indirectly quantified by combination of chemical stoichiometry and integration of their chemical labels. Attempt was made to make plausible explanations for the origins of these species. Finally, a mechanism with multiple step reactions process and double pathways was proposed. More than 90.7% of the total manganese source was accounted for at 9 h and meanwhile that of more than 91.4% of the total silicon source was accounted for.

关 键 词：氢硅烷化 积分定量 多步反应 双通道机理 

分 类 号：O643.32[理学—物理化学]