Polymerization by Transition Metal Complexes

A transition metal complex such as bpyNi(COD), generalized as LjNi, reacts with NCA in a complex reaction sequence that generates a propagating species XLV whose active center is a 5-membered amido-amidate metallacyclic complex. Propagation involves a nucleophilic attack by the amido nitrogen of the amido-amidate at the C-5 carbonyl of NCA. The 

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Polymerization by Transition-Metal Complex Catalysts. Mlly M12, and M13 have been polymerized by Et3Al/TiCl4 catalysts between 50° and 80 °C in n-hexane, the reaction times ranging from a few hours to several days. The polymers obtained have the same structure as those obtained by cationic polymerization. By analogy with mechanisms proposed in the literature (38, 39), the structure shown in Equation 24 may be proposed for the active center. 

Polymerization by Ziegler-Natta Catalysts. Polymerization by transition-metal complex catalysts gives oligomers of the same structures as those obtained cationically, with distinctly higher conversion degrees (Equation 29). 

Olefin polymerization by transition metal complexes such as those in the catalyst systems of Ziegler and Natta is remarkably stereospecific. A mixture of an alkylaluminum halide and TiCl4 polymerizes ethylene at low pressure to crystalline linear polyethylene 184) with a relatively high density (0.96) and melting point (132° C). These properties contrast sharply... 

Some of the vinyl monomers polymerized by transition metal benzyl compounds are listed in Table IX. In this table R represents the rate of polymerization in moles per liter per second M sec-1), [M]0 the initial monomer concentration in moles per liter (M) and [C]0 the initial concentration of catalyst in the same units. The ratio i2/[M]0[C]0 gives a measure of the reactivity of the system which is approximately independent of the concentration of catalyst and monomer. It will be observed that the substitution in the benzyl group is able to affect the polymerization rate significantly, but the groups that increase the polymerization rate toward ethylene have the opposite effect where styrene is concerned. It would also appear that titanium complexes are more active than zirconium. The results with styrene and p-bromostyrene suggests that substituents in the monomer, which increase the electronegative character of the double bond, reduces the polymerization rate. The order of reactivity of various olefinically unsaturated compounds is approximately as follows ... 

The catalytic transformation of olefins by transition metal complexes has received a great deal of attention during the past two decades. These catalytic reactions are important, especially industrially, because they represent some of the most economical ways to synthesize olefinic monomers or polymers. The more common types of these transformation reactions are (a) dimerization or polymerization of a-olefins (b) dimerization, oligomerization, cyclooligomerization, or polymerization of con-... 

Similarly, it was also found that radical polymerization was induced in the Ni(CO)3(PPh3)/CBrCl3 redox system [155]. This complex is soluble in the polymerization medium, and the polymerization proceeded in a homogeneous system. This redox iniferter system has been intensively developed to the recent successful living radical polymerization using transition-metal complexes in combination with alkyl halides by several independent research groups (see Sect. 6.2). 

SCBs and disilacyclobutanes are known to undergo ring-opening polymerization catalyzed by transition metal complexes including those of platinum, palladium, and rhodium <1965JOC2618>. Lappert and co-workers suggested that... 

Abstract The applications of hybrid DFT/molecular mechanics (DFT/MM) methods to the study of reactions catalyzed by transition metal complexes are reviewed. Special attention is given to the processes that have been studied in more detail, such as olefin polymerization, rhodium hydrogenation of alkenes, osmium dihydroxylation of alkenes and hydroformylation by rhodium catalysts. DFT/MM methods are shown, by comparison with experiment and with full quantum mechanics calculations, to allow a reasonably accurate computational study of experimentally relevant problems which otherwise would be out of reach for theoretical chemistry. 

Over the last 50 years numerous reactions of organic compounds catalyzed by transition metal complexes have been developed (e. g., olefin oxidation -Wacker Process, hydroformylation, carbonylation, hydrogenation, metathesis, Ziegler-Natta polymerization and oligomerization of olefins) in which the reactivity of metal-carbon bonds in the active intermediate (organometallics) is crucial. 

This paper has provided, we believe, a comprehensive, up-to-date, critical, and objective review on the discovery and the subsequent fast development of living radical polymerizations catalyzed by transition-metal complexes in the period from 1994 to early 2001. These metal-catalyzed living radical polymerizations have rapidly been developing since their discovery in 1994, and the scope of applicable monomers, metal catalysts, and initiators has been expanding. Their advantages include versatility toward a variety of monomers, feasibility in a wide range of reaction conditions, and relatively easy access to the materials. This permits many researchers to use the systems for the precision synthesis of various polymers with controlled architectures. 

This section summarizes the copolymerization of conjugated dienes with other monomers catalyzed by transition metal complexes. Some of the reactions here were also mentioned in the previous section. The catalyst CpTiCl3/MAO is active not only for the polymerization of 1,3-butadiene, isoprene, 1,3-pentadiene, and styrene but also for the copolymerization of these individual monomers [82]. 

Cationic Polymerization. In the compounds of Equation 25, the pseudoconjugation between the phenyl and the cyclopropane is maximum when the two rings are perpendicular (40). Polymerization, cationic or by transition-metal complex catalysts, indicates the participation of the phenyl group. 

In view of these observations it is not surprising that there occur a wide variety of catalytic reactions, particularly involving hydrocarbons. For example, the isomerization of olefins, homogeneous hydrogenations, group substitution in the vicinity of double bonds, and polymerization reactions are all catalyzed by transition metal complexes. 

Two mechanisms have been proposed for acetylene and substituted acetylene polymerization by transition metal catalysts one is the metal-alkyl mechanism and the other is the metal-carbene mechanism. In general, it has been proposed that the polymerization of acetylenes by Ziegler-Natta catalysts proceeds by the metal-alkyl mechanism, while the metal-carbene mechanism has been accepted for the polymerization of substituted acetylenes by metathesis catalysts whose main components are halides or complexes of group 5 and 6 transition metals. The latter will be discussed in Section III. 

The 1,2-insertion of alkenes into transition metal-carbon o-bond leads to C-C bond formation under mild conditions, as described in Chapter 6. This reaction is considered to be a crucial step in the coordination polymerization and carbometalation of alkenes catalyzed by transition metal complexes. A common and important carbometalation is the Heck-type arylation or vinylation of alkene catalyzed by Pd complexes [118], The arylation of alkene, most typically, involves the formation of arylpalladium species and insertion of alkene into the Pd-aryl bond as shown in Scheme 5.20. The arylpalladium species is formed by the oxidative addition of aryl halides to Pd(0) complexes or the transmetalation of aryl compounds of main group metals with Pd(II) complexes. Insertion of alkene into the Pd-aryl bond produces 2-arylalkylpalladium species whose y6-hydrogen elimination leads to the arylalkene. Oxidative chlorination of the 2-arylalkylpalladium intermediate forms chloroalkanes as the product. 

Living radical polymerization mediated by transition metal complexes is an area receiving an enormous amount of attention at present. Initial work reported by Sawamoto and Matyjaszewski has led to a huge development in novel catalysts, monomers and polymers. Catalysts based on Ru(II), > In Situ Spectroscopy of Monomer and Polymer Synthesis... 

The ATP process developed by Sawamoto and coworkers [226], uses an initiating system consisting of carbon tetrachloride, dichlorotri(triphenyl-phosphine)-ruthenium (II) and methylaluminum bis(2,6-di-fe/"f-butylphenoxide) to polymerize methyl methacrylate [226]. The polymerization involves reversible and homolytic cleavages of carbon-halogen terminal groups assisted by transition metal complexes [226]. 

Fig. 2.28. Mechanism of polymerization of ethylene by transition-metal complexes...

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