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合成了具有不同电子效应的 3种双膦配体 .其给电子性为 Ph2 P(CH2 ) 4 PPh2 >Ph2 P(O) (CH2 ) 4 PPh2 >Ph2 P(O) (CH2 ) 4 P(O) Ph2 .这 3种配体与醋酸铑二聚体配合物构成的催化剂 ,在混合辛烯的均相氢甲酰化反应中表现出的活性和选择性与配体给电子性强弱的次序完全相反 .我们认为 ,具有弱配位性的 [Rh(CH3COO) 2 ]2 Ph2 P-(O) (CH2 ) 4 P(O) Ph2 催化体系 ,因其形成的活性物种的活泼性高 ,有利于惰性的长碳链混合辛烯的活化转化 .对该体系循环使用的结果表明 ,经历 3次循环后 ,催化剂活性逐渐降低 .
Three kinds of bisphosphine ligands with different electronic effects were synthesized and their electronic properties were as follows: Ph2P (CH2) 4Ph2> Ph2P (O) (CH2) 4Ph2> Ph2P (O) ) Ph2. The catalyst composed of the three ligands and the rhodium acetate dimer complex shows the activity and selectivity in the homogeneous phase hydroformylation of the mixed octenes and the order of strong donor to electron donors In contrast, we believe that the [Rh (CH3COO) 2] 2Ph2P (O) (CH2) 4P (O) Ph2catalytic system with weakly coordinating structure Conducive to inert long-chain mixed octene activation transformation.The results of the system recycling shows that after three cycles, the catalyst activity gradually decreased.