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研究了Rh_4(CO)_(12)和[Rh(CO)_2Cl]_2两种铑原子簇合物在1—已烯氢甲酰化反应中的催化性能和反应前后催化剂溶液的红外光谱变化。结果表明,按加入的Rh_4(CO)_(12)和[Rh(CO)_2Cl]_2的分子数计算,前者的催化活性比后者高出一倍多;若按铑原子数计算,则二者活性较接近。红外光谱测定说明,Rh_4(CO)_(12)的簇结构反应前后无显著变化。然而,[Rh(CO)_2Cl]_2参与反应后却变成了以Rh_4(CO)_(12)为主的簇合物。反应过程中两种催化剂母体可能解离成类似的单核铑催化活性物种,反应之后,在常温常压下又聚合为簇合物。
The catalytic performance of Rh_4 (CO) _ (12) and [Rh (CO) _2Cl] _2 clusters in 1-hexene hydroformylation was investigated and the IR spectra of the catalyst solution before and after the reaction were studied. The results showed that the catalytic activity of the former was more than double that of the latter by the molecular weights of Rh_4 (CO) _ (12) and [Rh (CO) _2Cl] _2, The activity is closer. Infrared spectroscopy showed that there was no significant change in the cluster structure of Rh_4 (CO) _ (12) before and after the reaction. However, [Rh (CO) _2Cl] _2 became a cluster based on Rh_4 (CO) _ (12) after its reaction. During the reaction, the two catalyst precursors may dissociate into similar mononuclear rhodium catalytically active species, and after the reaction, polymerize into clusters at normal temperature and pressure.