铑膦络合催化剂活化过程的“原位”红外研究

“In Situ” Infrared Study on Activation Process of Rhodium Phosphine Complex

本文研究了正丁醛溶剂中Rh(acac)(CO)(Pph_(3))在不同条件下的活化过程及各种络合物间的转化关系,在反应条件下检出了活性组分,并发现活性组分会部分歧化为三羰基物与单羰基物。实验中检测到一些多羰基化合物,并发现体系生成的二聚物可分成无桥联与有桥联羰基两种络合物。

In butyl aldehyde solvent the activation prcccss of catalyst precusor Rh(acac)(CO)(Pph_(3)) under diffrent conditions and the transformation of various complexhave been studied. The active specks HRh(CO_(2))(Fph_(5))_(2) can be detected under reaction conditions, and its partial disproporlionation to HRh(CO)_(3)(Pph_(3)) and HRh-(CO)(Pph_(3))_(3) has been discovered. The results show that the dimer [Rh (CO)_(2)-(Pph_(3))_(2)]2 in the system may fall into two species Rh_(3)(CO)_(4)(Pph_(3))_(4) and (Pph_(3))_(3)-(CO)Rh(CO)_(2)Rh(CO)(Pph_(3))_(3) the latter is formed in higher CO pressure.