Abstract
Butadiene was found to oligomerize readily with bis(π-cycloocta-1,5-diene)nickel in alcohols, yielding linear conjugated and unconjugated dimers, trimers, and tetramers. The oligomers and their yields were affected by the solvents used. When primary alcohols, such as methyl, ethyl, and n-butyl, were used as the solvent, only small amounts of hydrooligomers were formed. On the other hand, in tert-butyl and isopropyl alcohols n-octa-1,6- and -2,6-diene and n-octa-1,3,6-triene were catalytically obtained, accompanied by small quantities of cyclododeca-1,5,9-triene, n-dodeca-1,6,10-triene, and n-hexadeca-2,6,10,14-tetraene. Addition of amines had little effect, except that diethylamine deactivated the catalysts. From the results of spectrometric analyses and pyrolysis of the nickel complex formed in the reaction of bis(π-cycloocta-1,5-diene)-nickel with butadiene in isopropyl alcohol, it has been deduced that the linear butadiene oligomers are formed through a complex composed of monomeric butadiene, butadiene oligomer, isopropoxy group, and nickel atom.
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Yamazaki, N., Ohta, T. Oligomerization of Butadiene with Bis(π-cycloocta-1,5-diene)Nickel in Alcohols. Polym J 4, 616–622 (1973). https://doi.org/10.1295/polymj.4.616
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DOI: https://doi.org/10.1295/polymj.4.616