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含氮双齿膦配体(Ph2PCH2)2NCH2CH2OCH2CH2NHCH2CH2PO3Na2(以A表示)在1-十二烯的氢甲酰化反应中的实 验结果表明双膦配体的螯合作用降低了催化活性以及双膦-铑配合物有利于直链醛的生成.A与油溶性催化剂 HRh(CO)(PPh3)3在合成气氛下发生配体交换形成配合物HRh(CO)(A)(PPh3),其催化活性比单膦-铑配合物的催化活性更 低.由于双膦与铑配位后形成的络合物中铑的配位空间更拥挤,因此1-十二烯的端碳原子更容易与铑中心络合配位,形 成直链烷基-铑络合物,使得产物醛中直链醛的含量增大.
The experimental results in the hydroformylation reaction of 1-dodecene containing nitrogen-containing bidentate phosphine ligands (Ph2PCH2) 2NCH2CH2OCH2CH2NHCH2CH2PO3Na2 (indicated as A) indicate that the chelation of the bisphosphine ligand reduces the catalytic activity and that the diphosphine-rhodium The complex is beneficial to the formation of linear aldehydes, and the complex of HRh (CO) (PPh3) 3 and oil-soluble catalyst HRh (COh) (PPh3) 3 undergoes ligand exchange in the synthesis atmosphere to form the complex HRh (CO) Phosphine-rhodium complexes with lower catalytic activity.Because the coordination space between rhodium and rhodium in the complex formed by the double phosphine is more crowded, the terminal carbon atoms of 1-dodecene more easily complex with the rhodium center Coordination, the formation of linear alkyl-rhodium complex, so that the product aldehyde aldehyde content increased.