【摘要】 用量子化学 AMI方法优化了 1 -苯基二苯并膦二磺化产物 ( PDBPDS)和三磺化三苯基膦 ( TPPTS)的几何构型 .比较两种化合物的空间结构和电子结构发现 ,在氢甲酰化铑膦催化反应体系中 ,PDBPDS的配体性能优于 TPPTS.首次研究了以 PDBPDS为配体的铑膦催化剂对丙烯氢甲酰化反应的催化性能 ,考察了反应温度、压力、膦铑物质的量比和搅拌速度对催化活性和选择性的影响 .结果表明 ,在 2 .0 MPa,1 0 0℃ ,膦铑物质的量比为 35 ,搅拌速度为 5 0 0 r/min及 V( H2 ) /V( CO) =1 /1的条件下 ,催化活性可达到 2 80 0 g(丁醛 ) /[g(铑 )·h],正异构产物物质的量比为 1 2 .3,在相同条件下与传统的三磺化三苯基膦 ( TPPTS)为配体的铑膦催化剂相比 ,催化活性和选择性提高了 2倍 .反应结束后 ,有机相和水相分离简单 ,有机相铑浓度仅为3.6× 1 0 - 8mol/L,有效地解决了铑流失问题 ,表明 PDBPDS是极具开发前景的新型水溶性配体更多还原

【Abstract】 Structures of 1 phenyldibenzophosphole disulfonate(denoted as PDBPDS) and triphenylphosphorus trisulfonate(denoted as TPPTS) were optimized by using quantum chemical AM1 method. Both stereo and electronic structure show that PDBPDS acts as a better ligand than TPPTS in the Rh/P catalyst system of hydroformylation. The performance of the novel ligand PDBPDS in water soluble Rh complex, HRh(CO)(PDBPDS) 3, was conducted in biphasic hydroformylation of propylene. The influences of reaction parameters such as reaction temperature, n (PDBPDS)/ n (Rh) and agitating speed on catalytic properties were investigated. The result shows that under the condition of 2.0 MPa, 100 ℃, n (PDBPDS) / n (Rh)=35, agitating speed 500 r/min and V (H 2)/ V (Co)=1/1, TON is 2 800 g(butyraldehyde)/ and the n (normal)/ n (iso) reaches 12.3, concentration of Rh in the organic phase is only 3.6×10 -8 mol/L. Compared with the performance of TPPTS under the same condition, both activity and selectivity are remarkably improved. Further, the catalyst can be easily separated from the reaction system.更多还原