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The Effect of Metal‐Ligand Affinity on Fe 3 O 4 _ Supported Co–Rh Catalysts for Dicyclopentadiene Hydroformylation
Author(s) -
Ma Yubo,
Qing Shaojun,
Li Nana,
Zhang Letao,
Li Shouzhu,
Gao Zhixian,
Li Hongyi,
Eli Wumanjiang,
Wang Tianfu
Publication year - 2015
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20933
Subject(s) - hydroformylation , chemistry , phosphine , dicyclopentadiene , catalysis , selectivity , ligand (biochemistry) , rhodium , syngas , thermogravimetry , thermal decomposition , inorganic chemistry , medicinal chemistry , organic chemistry , polymerization , biochemistry , polymer , receptor
The catalytic performances of Co‐Rh/Fe 3 O 4 catalysts modified with phosphine ligands (PPh 3 ) and its analogues on dicyclopentadiene hydroformylation were evaluated. Among these catalysts, Co‐Rh/Fe 3 O 4 modified with tris( p ‐trifluoromethylphenyl)phosphine was determined to be effective for monoformyltricyclodecanes production, whereas Co‐Rh/Fe 3 O 4 modified with PPh 3 or tri‐ p ‐tolylphosphine was effective for the diformyltricyclodecanes production. To investigate the ligand effects, the complex catalyst system (Co‐Rh/Fe 3 O 4 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 PPh 3 series, experiments with other ligands also demonstrated similar selectivity trends.