烯烃氢甲酰化催化剂活性物种的原位~1H NMR研究  

in situ ~1H NMR Study of Active Species of Hydroformylation Catalyst

作　　者：李达刚[1] 夏春谷[1] 孙衍文[1] 杨薇曼 

机构地区：[1]中国科学院兰州化学物理研究所,甘肃兰州730000

出　　处：《物理化学学报》1996年第1期71-74,共4页Acta Physico-Chimica Sinica

摘　　要：The rhodium-phosphine complex catalyst Rh(CO)(acac)(PPh3)(Ⅰ) for 1-hexene hydroformylation was studied under the following reaction conditions: CO/H2=1(mole rate), pressure 1.0 MPa, temperature 25-120℃, by using the pres surized in-situ 1H NMR technique. Experimental results indicated that the formation of a rhodium hydride complex from (Ⅰ) began at room temperature and its amount increased with increasing of reaction temperature. This intermediate complex began to decompose at 100℃ and disapeared completely at 120℃ The intensity change of the proton signal was parallel to catalytical activity in hydroformylation of olefins. Under pure CO pressure the proton signal of Rh-H bond was not observed. There was a 0.2 ppm difference in proton chemical shifts of Rh-H bond under pure H2 pressure and under H2+CO pressure. The results showed that the rhodium-hydride carbonyl complex is the active intermediate in the industrial hydroformylation process.The rhodium-phosphine complex catalyst Rh(CO)(acac)(PPh3)(Ⅰ) for 1-hexene hydroformylation was studied under the following reaction conditions: CO/H2=1(mole rate), pressure 1.0 MPa, temperature 25-120℃, by using the pres surized in-situ 1H NMR technique. Experimental results indicated that the formation of a rhodium hydride complex from (Ⅰ) began at room temperature and its amount increased with increasing of reaction temperature. This intermediate complex began to decompose at 100℃ and disapeared completely at 120℃ The intensity change of the proton signal was parallel to catalytical activity in hydroformylation of olefins. Under pure CO pressure the proton signal of Rh-H bond was not observed. There was a 0.2 ppm difference in proton chemical shifts of Rh-H bond under pure H2 pressure and under H2+CO pressure. The results showed that the rhodium-hydride carbonyl complex is the active intermediate in the industrial hydroformylation process.

关 键 词：活性物种 NMR1 氢甲酰化 催化剂 

分 类 号：O643.361[理学—物理化学] O641.133[理学—化学]