顺丁烯二酸酐均相配位催化氢化反应研究

A Study on the Homogeneous Hydrogenation of Maleic Anhydride Catalyzed by Some Transition Metal Complexes

研究了在室温和大气压力下，几种过渡金属络合物对顺丁烯二酸酐（简称顺酐）氢化生成琥珀酸酐的催化活性．实验结果表明，它们的催化活性顺序是：ＰｄＣｌ２（ＰｈＣＨ２ＣＮ）２＞ＲｕＣｌ２（ＰＰｈ３）３＞ＰｄＣｌ２（ＰｈＣＮ）２＞ＰｄＣｌ２（ＰＰｈ３）２ＲｈＣｌ（ＰＰｈ３）３．在所应用的反应条件下（催化剂与底物摩尔比：５％；溶剂：苯；时间：２ｈ），其中催化活性最高的络合物，ＰｄＣｌ２（ＰｈＣＨ２ＣＮ）２，给出了琥珀酸酐的产率高达９３．０％．研究了在适当温度和压力下（３７３Ｋ，１５００ｋＰａＨ２），另外几种具有相同配体的络合物在该反应中的催化活性．它们的催化活性顺序为：ＲｕＣｌ２（ＰＰｈ３）３＞ＲｈＣｌ（ＰＰｈ３）３＞ＮｉＣｌ２（ＰＰｈ３）２＞ＣｏＣｌ２（ＰＰｈ３）２＞ＦｅＣｌ２（ＰＰｈ３）２＞ＰｄＣｌ２（ＰＰｈ３）２．这恰好与这些络合物中的中心金属原子的电离势大小顺序是一致的．在这些络合物中，ＮｉＣｌ２（ＰＰｈ３）２不仅对该反应有较高的催化活性，且中心金属不是贵金属，将其重复使用５次。

At room temperature and atmospheric pressure, the homogeneous catalytic activity of some transition metal complexes for maleic anhydride hydrogenation to succinic anhydride has been studied. The results of the experiments show that their catalytic activity decreases in the following order: PdCl 2(PhCH 2CN) 2>RuCl 2(PPh 3) 3>PdCl 2(PhCN) 2>PdCl 2(PPh 3) 2～RhCl(PPh 3) 3. Under the conditions employed (catalyst/substrate mol ratio: 5%, solvent: benzene, time: 2 h), the most active complex among them, PdCl 2(PhCH 2CN) 2, gives yield of succinic anhydride as high as 93 0%. At somewhat higher temperature and pressure (373 K, 1500 kPa H 2), the homogeneous catalytic activity of several other transition metal complexes with the same ligands has also been investigated for the reaction. The sequence of their catalytic activity is as follows: RuCl 2(PPh 3) 3>RhCl(PPh 3) 3>NiCl 2(PPh 3) 2>CoCl 2(PPh 3) 2>FeCl 2(PPh 3) 2>PdCl 2(PPh 3) 2, which is the same as their central metal atoms′ ionization potentials. The complex NiCl 2(PPh 3) 2, which has high catalytic activity for the reaction and whose cental metal is not noble, was recycled five times, and its catalytic activity did not diminish appreciably.