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用Rh_2(CO)_4Cl_2与水杨醛肟的钠盐反应合成了二羰基水杨醛肟铑配合物Bh(sox)(CO_2)(1)。在常压下研究了该配合物与膦或亚磷酸酯组成的体系对苯乙烯氢甲酰化反应的催化性能,此体系对烯烃没有催化加氢作用,产物醛的化学选择性均为100％。考察了膦的结构与用量对催化活性和选择性的影响,双膦作配体时活性和选择性都高于单膦,其中Rh(sox)(CO)_2-Ph_2P(CH_2)_3PPh_2体系的最高初活性(TON)可达1.60min~(-1),2-苯基丙醛的选择性在90％以上。对反应的活性物种作了初步讨论。
Synthesis of Bh (sox) (CO_2) (1) with Rhodium (CO) _4Cl_2 and Salicylaldoxime Sodium Salt. Under atmospheric pressure, the catalytic activity of the complex with phosphine or phosphite on the hydrogenation of styrene was studied. The catalytic hydrogenation of the olefin was not observed. The chemical selectivity of the aldehyde was 100% . The effects of the structure and amount of phosphine on the catalytic activity and selectivity were investigated. The activity and selectivity of phosphine ligand were higher than that of monophosphine. The highest Rh (sox) (CO) _2-Ph_2P (CH_2) _3PPh_2 system Initial activity (TON) up to 1.60min ~ (-1), 2-phenylpropionaldehyde selectivity in more than 90%. The active species of the reaction was preliminarily discussed.