The Effect of Metal‐Ligand Affinity on Fe3O4_Supported Co–Rh Catalysts for Dicyclopentadiene Hydroformylation |
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| Authors: | Yubo Ma Shaojun Qing Nana Li Letao Zhang Shouzhu Li Zhixian Gao Hongyi Li Wumanjiang Eli Tianfu Wang |
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| Institution: | 1. Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi, People's Republic of China;2. Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, People's Republic of China;3. University of the Chinese Academy of Sciences, Beijing, People's Republic of China;4. Xinjiang Quality of Products Supervision & Inspection Institute of Technology, Urumqi, People's Republic of China;5. Department of Power Engineering, Xinjiang Institute of Engineering, Urumqi, People's Republic of China |
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| Abstract: | The catalytic performances of Co‐Rh/Fe3O4 catalysts modified with phosphine ligands (PPh3) and its analogues on dicyclopentadiene hydroformylation were evaluated. Among these catalysts, Co‐Rh/Fe3O4 modified with tris(p‐trifluoromethylphenyl)phosphine was determined to be effective for monoformyltricyclodecanes production, whereas Co‐Rh/Fe3O4 modified with PPh3 or tri‐p‐tolylphosphine was effective for the diformyltricyclodecanes production. To investigate the ligand effects, the complex catalyst system (Co‐Rh/Fe3O4 and phosphine ligand) was subjected to pretreatment with syngas and then characterized by thermogravimetry and differential thermal analysis (TG‐DTA). It was determined that the threshold decomposition temperature reflected the corresponding Rh‐phosphine interaction strength, affecting the catalytic selectivity toward different products. A weak Rh‐phosphine interaction was desirable to produce monoformyltricyclodecanes with fast reaction kinetics, whereas a strong Rh‐phosphine complex was required for the synthesis of diformyltricyclodecanes. In addition to the selectivity rule shown in the PPh3 series, experiments with other ligands also demonstrated similar selectivity trends. |
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