Ethylene-butadiene codimerization

In this codimerization reaction, the predominant complex is 3, which should lead to the ethylene-butadiene codimerization product. If the ethylene in complex 3 is displaced by butadiene to form 7 before the insertion reaction takes place, then a C8 or higher olefin could be formed... 

The purpose of the ethylene-butadiene codimerization process is to produce rrmns-1,4-hexadiene from ethylene and butadiene, as shown in reaction (S.6S). The product is an important monomer in synthetic rubber production. 

Butadiene and ethylene are codimerized with a soluble rhodium-phosphine complex as the catalyst. Very little has been reported on the mechanistic evidence for this reaction. However, a catalytic cycle as shown in Fig. 7.9 involving a rhodium hydride seems likely. Reducing rhodium trichloride with ethanol in the presence of a tertiary phosphine generates the hydride complex 7.32. The 1,4-hydride attack on the coordinated butadiene gives an rf-allyl complex. This is shown by the conversion of 7.33 to 7.34. Ethylene coordination to 7.34 produces 7.35. 

Butadiene and ethylene will codimerize to give c -l,4-hexadiene in the presence of cobalt (Henrici-Olive and Olive, 1972) or rhodium catalysts [Eq. (87) (Alderson et al., 1965)]. The 2,4-hexadiene formed presumably arises by isomerization of the 1,4-diene. 

The codimerization reaction we will discuss in this chapter belongs to the last type. The reaction and the reactants involved will be the simplest of them all, i.e., a 1 1 codimerization of ethylene and butadiene to form C dienes. 

Typical Isomer Distributions in 1 1 Codimerization of Ethylene and Butadiene by Various Transition Metal Catalysts... 

Scheme 2. Catalytic cycle for Rh catalyst for 1 1 codimerization of ethylene and butadiene to form 1,4-hexadiene.

The rate equation for the dimerization of ethylene (5) can be used to describe the codimerization in the presence of large excesses of butadiene. The rate of the addition reaction as measured by the disappearance of ethylene is represented in Eq. (5). It is first order in ethylene, proton, chloride, and rhodium. 

Hexadiene is the immediate product found in the codimerization reaction described above in a mixture of ethylene and butadiene. However, the reaction will not stop at this stage unless there is an overwhelming excess of butadiene and an adequate amount of ethylene present. As the conversion of butadiene increases, some catalyst begins to isomerize... 

The essential steps in the nickel-catalyzed 1 1 codimerization reaction, which involve hydride addition to butadiene and ethylene coordination to the metal atom, were first proposed by Kealy, Miller, and Barney (35) and were later demonstrated by Tolman (40) using a model complex. Tolman prepared the complex H—Ni+L PFe [L = (EtO)3P] and showed that, after prior dissociation to form H—NiL3, it can react with butadiene to form a 7r-crotyl complex 19. 

The results on Pd complexes as catalyst for the 1 1 codimerization are very limited at this time (85-87). Schneider (85, 86) found that palladous chloride in conjunction with dibutylaluminum chloride catalyzes the formation of exclusively trans-1,4-hexadiene as the 1 1 codimerization product of ethylene and butadiene. A vyn-7r-crotylpalladium complex was postulated as the key intermediate. The criterion for selectivity toward... 

---