物理化学学报 >> 1996, Vol. 12 >> Issue (01): 71-74.doi: 10.3866/PKU.WHXB19960116
Li Da-Gang,Xia Chun-Gu,Sun Yan-Wen,Yang Wei-Man
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 pressurized 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 Ph-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.
李达刚,夏春谷,孙衍文,杨薇曼. 烯烃氢甲酰化催化剂活性物种的原位1H NMR研究[J]. 物理化学学报, 1996, 12(01): 71-74.
Li Da-Gang,Xia Chun-Gu,Sun Yan-Wen,Yang Wei-Man. in situ 1H NMR Study of Active Species of Hydroformylation Catalyst[J]. Acta Phys. -Chim. Sin., 1996, 12(01): 71-74.
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