Conclusions
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1.
The catalytic system Et2AlCN (II)-[Ph3P]2Rh(CO)Cl (I) was studied in the oligomerization and polymerization of 1,3-butadiene.
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2.
From the catalytic system were isolated and characterized the following complexes: [Ph3P]Rh(CO)Cl-NCAlEt2 (III), [Ph3P][Et2Al]Rh(CO)(CN)Cl·NCAlEt2 (IV), [Ph3P]Et2Al]Rh(CO)(CN)2 (V), and [Ph3P]RhH(Me2NHCO)(CN)2 (VI).
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3.
When (II) is reacted with (I), the triphenylphosphine is first replaced by diethylcyanalan, followed by oxidative addition to Rh(I) with cleavage of the Al-CN bond.
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4.
The direction of the catalytic reaction depends on the composition of the complexes and the medium: the cyclic oligomers, 4-vinyl-1-cyclohexene and 1,5-cyclooctadiene, are formed in DMF and pyridine solutions, while the cis- or trans-polybutadienes are formed in ethanol solution.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 137–143, January, 1981.
The authors express their deep gratitude to M. L. Khidekel for his interest in the work and valuable discussion of the results, and to L. A. Komarova for synthesizing the starting compounds.
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Korableva, L.G., Lavrent'ev, I.P. Activation of Rh(I) phosphinecarbonyl complexes in ziegler-type systems in reaction with 1,3-butadiene. Russ Chem Bull 30, 115–121 (1981). https://doi.org/10.1007/BF00962266
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DOI: https://doi.org/10.1007/BF00962266