TY - JOUR
T1 - Rhodium(I)-catalyzed alternating co-oligomerization of carbon monoxide with olefins
T2 - Synthetic and mechanistic studies
AU - Sen, Ayusman
AU - Brumbaugh, Jeffrey S.
AU - Lin, Minren
N1 - Funding Information:
This research was supported by a grant from the U.S. Department of Energy, O&e of Basic Energy Sciences (DEE-FGO2-S4ER13295). We also thank Johnson-Matthey, Inc., for a generous loan of rhodium.
PY - 1992/6
Y1 - 1992/6
N2 - Rhodium(I) phosphine complexes were found to catalyze the alternating co-oligomerization of ethylene and carbon monoxide in appropriate solvents. In a mixture of alcohol (ROH) and acetic acid, the products were H(CH2CH2CO)nCH2CH3 and H(CH2CH2CO)nOR (n= 1-4). Only the oligomeric polyketones were formed when a mixture of alcohol and water was used as the solvent. The effect of solvent composition and additives on the product distribution was studied extensively. The reactions were initiated by a rhodium-hydride species formed through the water-gas shift reaction. The chain growth involved the alternate insertions of ethylene and carbon monoxide into the initial rhodium-hydride bond. The oligomeric polyketoesters were formed by the alcoholysis of the intermediate rhodium-acyl species, whereas the oligomeric polyketones were generated through a bimolecular reductive elimination from the intermediate rhodium alkyls and a rhodium hydride. The catalyst system was also found to effect the carbonylation of propylene and butene.
AB - Rhodium(I) phosphine complexes were found to catalyze the alternating co-oligomerization of ethylene and carbon monoxide in appropriate solvents. In a mixture of alcohol (ROH) and acetic acid, the products were H(CH2CH2CO)nCH2CH3 and H(CH2CH2CO)nOR (n= 1-4). Only the oligomeric polyketones were formed when a mixture of alcohol and water was used as the solvent. The effect of solvent composition and additives on the product distribution was studied extensively. The reactions were initiated by a rhodium-hydride species formed through the water-gas shift reaction. The chain growth involved the alternate insertions of ethylene and carbon monoxide into the initial rhodium-hydride bond. The oligomeric polyketoesters were formed by the alcoholysis of the intermediate rhodium-acyl species, whereas the oligomeric polyketones were generated through a bimolecular reductive elimination from the intermediate rhodium alkyls and a rhodium hydride. The catalyst system was also found to effect the carbonylation of propylene and butene.
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U2 - 10.1016/0304-5102(92)80084-T
DO - 10.1016/0304-5102(92)80084-T
M3 - Article
AN - SCOPUS:0026876236
SN - 0304-5102
VL - 73
SP - 297
EP - 323
JO - Journal of Molecular Catalysis
JF - Journal of Molecular Catalysis
IS - 3
ER -