水溶性铑-膦络合物催化烯烃氢甲酰化反应--阳离子表面活性剂的加速作用

介绍了以水溶性铑-膦络合物RhCl(CO)(TPPTS)₂作为催化剂前体在水/有机两相体系中催化烯烃氢甲酰化反应研究的进展，阐述了阳离子表面活性剂的加速作用和介稳态胶束-离子对协同作用机理关系.通过两相体系中界面分子组装和选择与烯烃分子链长相匹配的表面活性剂, 设计制备了高区域选择性复合催化剂体系.当采用双长链表面活性剂与铑-膦络合物组成的复合催化体系时，在不搅拌的情况下就显示出极高的催化活性.

OLEFIN HYDROFORMYLATION CATALYZED BY WATER-SOLUBLE RHODIUM COMPLEXES--ACCELERATION BY CATIONIC SURFACTANT

The studies of olefin hydroformylation in aqueous/organic bi-phase catalyzed by water soluble RhCl(CO)(TPPTS)₂-cationic surfactant complex system was introduced.The acceleration of the reaction by cationic surfactant was connected with the mechanism of meta-stable micellar-ionic pair synergistic action.The enrichment of rhodium catalyst on the micellar interface and solubilization of olefin in hydrophobic core of micelle created a very favorable microcircumstance for olefin coordination with rhodium complex.Therefore the high region-selective and high active rhodium catalyst systems could be designed and prepared by molecular assembly on biphasic interface.The modification of catalytic performance of rhodium complex was realized by the application of CTAB-SDS mixed surfactants and TPPTS-TPPDS mixed ligands.TOF(turnover frequency,h^-1)and normal/isomer aldehyde ratio (n/i)in 1-dodecene hydroformylation catalyzed by the modified rhodium catalyst reached 200—350 h^-1 and 18—40,respectively.The matching effect between chain length of olefin and surfactant was discovered.If both the chains length were similar the catalyst had high region-selectivity.When cationic surfactant with double long chain combined with water soluble rhodium phosphine complex, the catalyst system exhibited high activity and TOF of 1-dodecene hydroformylation could reach over 1000 h-1 even without stirring.