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用量子化学 AM1方法优化了 1-苯基二苯并膦 (PDBP)和三苯基膦 (TPP)的几何构型 ,比较了两种化合物的电子结构和空间结构 ,发现 PDBP作为羰基合成铑膦催化剂的配体要优于三苯基膦 (TPP) ;系统研究了 PDBP的合成方法 ,其最佳合成条件为 :在无水无氧的条件下 ,采用二乙胺锂与溴化四苯基膦摩尔比为 3,反应温度为2 2℃ ,反应 5 h,反应后酸化 ,p H值为 1～ 2 ,产物收率可达到 85 %～ 88% .采用元素分析、红外、核磁等方法 ,对其结构进行了表征 ,并将 PDBP用于丙烯氢甲酰化反应的催化剂配体 .实验证明 ,在相同的反应条件下 ,以其为配体的催化剂活性约是目前工业上使用的以三苯基膦为配体的催化剂的 1.2倍 ,选择性约为其 1.7倍 .
The geometries of 1-phenyldibenzophosphine (PDBP) and triphenylphosphine (TPP) were optimized by the quantum chemistry AM1 method. The electronic structures and spatial structures of the two compounds were compared and PDBP was synthesized as a carbonyl-containing rhodium phosphine The ligand of the catalyst was superior to triphenylphosphine (TPP). The synthesis of PDBP was studied systematically. The optimum conditions for the synthesis of PDBP were as follows: lithium diethylamine and tetraphenylphosphonium bromide Phosphine molar ratio of 3, reaction temperature of 22 ℃, the reaction for 5 h, the reaction acidification, p H value of 1 to 2, the product yield can reach 85% to 88%. Using elemental analysis, infrared, NMR and other methods, Its structure was characterized and PDBP was used as the catalyst ligand for the propane hydroformylation.It was proved that the activity of the catalyst with its ligand was about 3 The phenylphosphine ligand was 1.2 times the catalyst, the selectivity of about 1.7 times.