Ethylene complexes polymerization

Boratabenzene complexes of Group 3 and Group 6 metals serve as effective catalysts for the oligomerization/polymerization of ethylene. For example, [(C5H5B-Ph)2ScPh]2, pretreated with H2, oligomerizes ethylene to furnish 1-alkenes.17a In the case of a Cr(III)-boratabenzene complex, ethylene is polymerized to afford... 

The course of stereospecific olefin polymerization was studied by using the molecular mechanics programs, MM-2 and Biograph, based on the optimized geometries of the ethylene complex and the transition state [13,203]. Interestingly, the steric interaction at the transition state mainly controls the stereochemistry in polymerization, which proceeds specifically isotactic or syndiotactic depending on the kind of catalyst. 

Figure 6. Ethylene complex (Ilia) and insertion transition state TS[IIIa-IVa] for the polymerization process involving la (or Ila)...

The transition group compound (catalyst) and the metal alkyl compound (activator) form an organometallic complex through alkylation of the transition metal by the activator which is the active center of polymerization (Cat). With these catalysts not only can ethylene be polymerized but also a-olefins (propylene, 1-butylene, styrene) and dienes. In these cases the polymerization can be regio- and stereoselective so that tactic polymers are obtained. The possibilities of combination between catalyst and activator are limited because the catalytic systems are specific to a certain substrate. This means that a given combination is mostly useful only for a certain monomer. Thus conjugated dienes can be polymerized by catalyst systems containing cobalt or nickel, whereas those systems... 

We have already seen in Section 2.2.2 that metal-alkyl compounds are prone to undergo /3-hydride elimination or, in short, /3-elimination reactions (see Fig. 2.5). In fact, hydride abstraction can occur from carbon atoms in other positions also, but elimination from the /8-carbon is more common. As seen earlier, insertion of an alkene into a metal-hydrogen bond and a /8-elimination reaction have a reversible relationship. This is obvious in Reaction 2.8. For certain metal complexes it has been possible to study this reversible equilibrium by NMR spectroscopy. A hydrido-ethylene complex of rhodium, as shown in Fig. 2.8, is an example. In metal-catalyzed alkene polymerization, termination of the polymer chain growth often follows the /8-hydride elimination pathway. This also is schematically shown in Fig. 2.8. 

The phosphine-stabilized ethylene complex of zirconocene(n) reacts with 1 equiv. of B(G6F5)3 to form the girdle-type zwitterionic complex 754 (Equation (49)).574 Both the solution and solid-state structures of 754 feature a strong f3-CH agostic interaction. The zwitterion 754 is a single-component catalyst for the polymerization of ethylene under ambient conditions, although for optimal activity an additional equivalent of B(G6F5)3 is needed. 

Alkene complexes of Ti, Zr and Hf have been intensively investigated with regard to the nature of bonding and the close relation to olefin oligomerization and polymerization. Alkene complexes of zirconocene and hafnocene are isolated as the trimethylphosphine adduct, Cp2M(T -alkene)(PMe3) (33) [92-94]. Cp 2Ti(CH2=CH2) (34) is a 16 electron ethylene complex with a rich reaction chemistry as summarized in Scheme 6.4 [95-99]. The reaction profile of 34 indicates that the metallacyclopropane canonical form makes an important contribution [100]. 

These complexes lead to a considerable increase of the Interlonlc distance In the ion pairs and It has been shown that such ligands have a marked activating effect on anionic polymerizations (14,15, 16). Moreover, the aggregates are destroyed and simple kinetic results have been obtained in the case of propylene sulfide and ethylene oxide polymerizations (12). 

C3-symmetrical tripodal ligands have been used to obtain amido complexes of family (86). If chiral substituents are present in the ligand periphery, some stereo discrimination is observed in the reaction with several chiral ketones and aldehydes. On the other hand, such systems can generate early-late heterobimetallics with metal-metal bonds (equation 41). Reaction of (91) with MeNC as well as the heteroallenes CO2, CS2, RNCO and RNCS led to insertion into the polar metal-metal bond. Tris (pyrazolyl) borate see Tris(pyrazolyI)borates) Zr and Hf complexes are other interesting examples of the type (86). In combination with MAO, they give promising results in ethylene and ethylene/hexene polymerizations. Substitution of these sterically crowded ligands allows adjustements of the environment of the active site to the... 

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