THE MECHANISM OF PHOSPHINE-MODIFIED RHODIUM-CATALYZED HYDROFORMYLATION STUDIED BY CIR FTIR

被引:151
作者
MOSER, WR [1 ]
PAPILE, CJ [1 ]
BRANNON, DA [1 ]
DUWELL, RA [1 ]
WEININGER, SJ [1 ]
机构
[1] WORCESTER POLYTECH INST,DEPT CHEM,WORCESTER,MA 01609
来源
JOURNAL OF MOLECULAR CATALYSIS | 1987年 / 41卷 / 03期
关键词
ALDEHYDES - Chemical Reactions - AROMATIC COMPOUNDS - Synthesis - CATALYSIS - CHEMICAL REACTIONS - Reaction Kinetics - SPECTROSCOPY; INFRARED; -; Applications;
D O I
10.1016/0304-5102(87)80106-2
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The mechanism of phosphine-modified rhodium-catalyzed hydroformylation of 1-hexene was studied by in situ infrared spectroscopy using high pressure autoclaves equipped with embedded cylindrical internal reflectance crystals (CIR-FTIR). A series of RhH(CO)//2(PR//3)//2 complexes were synthesized using p-substituted triarylphosphines where the electron density on rhodium was varied by using p-N(CH//3)//2, p-OCH//3, p-H, p-F, p-Cl or p-CF//3. The metal carbonyl and metal hydride infrared stretching frequencies were correlated by a standard Hammett treatment of the data. Reaction rates and selectivities for linear aldehydes both increased with increasingly electron-withdrawing phosphines. The rate and spectroscopic data permitted the assignment of a reaction mechanism involving CO dissociation from RhH(CO)//2L//2 as the primary selective hydroformylation pathway.
引用
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页码:271 / 292
页数:22
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