Polymerization metal-catalyzed-coupling reactions

As outlined earlier, three methods of polymerization have been established for the preparation of thiophenes, viz. electrochemical polymerization [189, 190], oxidative chemical polymerization using Lewis acid catalysts such as FeCl3 [191,192], and step-growth condensation polymerization using transition metal-catalyzed coupling reactions [lj]. 

Transition metal catalyzed coupling reactions of aromatic halides, such as Heck or Suzuki coupling, are used extensively for the synthesis of low-molecular-weight organic compounds. With bifunchonal substrates, polymers can be obtained. By contrast to all other polymerization reactions considered in this chapter, such reactions represent step-growth-type polymerizations. 

Polymerization of thiophenes can be carried out in many different ways and the most commonly used methods can be generalized into three categories (i) electropolymerization, (ii) metal-catalyzed coupling reactions and (iii) chemical oxidative polymerization. Electropolymerization is a widely used method to prepare insoluble films of PTs and represents a simple and efficient way to study the optical and electronic properties of PTs [4], although it is rarely used in the preparation of electroluminescent materials. In 1980, Yamamoto et al. reported the Ni-catalyzed polycondensation of 2,5-dibromothiophene 1. The latter was allowed to react with Mg in THF, affording 2-magnesiobromo-5-bromothiophene 2, which in the presence of Ni(bipy)Cl2 (bipy = 2,2 -bipyridyl) produced PT 3 (Scheme 19.2) [15], In the same year, Lin and Dudek described another example of a metal-catalyzed route to unsubstituted PT 3, exploiting acetylacetonates of Ni, Pd, Co and Fe as catalysts [16]. 

This chapter will briefly review the fundamental organometallic reactions that play a key role in almost all metal-catalyzed processes. It will then apply these reaction steps to explain currently accepted mechanisms for some major catalytic cycles hydrogenation, hydroformylation, methanol carbonylation, Pd-catalyzed coupling reactions, and alkene polymerization and metathesis. Each of these catalytic reactions is covered in considerably more detail in later chapters, so the discussion here will be limited to relating and using the various fundamental reactions to build up and describe multistep catalytic cycles. 

The insertion of olefins into metal-alkyl linkages is the cornerstone of the preparation of polyolefins and a-olefins, and the insertions of olefins into metal-aryl bonds is one step of a common class of palladium-catalyzed coupling reactions (the Mizoroki-Heck reaction). The insertions of olefins into early-metal-alkyl bonds is part of the so-called Cos-see mechanism of Ziegler-Natta olefin polymerization and of Cramer s mechanism for olefin dimerization. The following sections present examples of these insertion reactions and information on the mechanisms of this type of C-C bond formation. 

Palladium-catalyzed coupling reactions play a vital role in the synthesis of CPEs. Similar to most transition-metal-catalyzed reactions, it is important to eliminate oxygen by degassing the solution with argon or nitrogen. Typically, the polymerization of CPEs is carried out in polar solvents such as DMF, THF and MeOH water can be used as a cosolvent to improve the solubility of the... 

Transition metal catalyzed coupling polymerization The most popular method for the s)mthesis of BDT based conjugated polymers takes advantage of the well-developed transition-metal mediated coupling reactions, featuring mild reaction conditions, remarkable functional group tolerance and high yields (Scheme 3.6). 

Pu and co-workers incorporated atropisomeric binaphthols in polymer matrixes constituted of binaphthyl units, the macromolecular chiral ligands obtained being successfully used in numerous enantioselective metal-catalyzed reactions,97-99 such as asymmetric addition of dialkylzinc reagents to aldehydes.99 Recently, they also synthesized a stereoregular polymeric BINAP ligand by a Suzuki coupling of the (R)-BINAP oxide, followed by a reduction with trichlorosilane (Figure 10).100... 

Dehydrogenative Coupling. Transition-metal catalyzed polymerization of silanes appears to hold promise as a viable route to polysilanes. A number of transition-metal complexes have been investigated, with titanium and zirconium complexes being the most promising (105—108). Only primary silanes are active toward polymerization, and molecular weights are rather low. The dehydrogenative polymerization is depicted in reaction 11, where Cp = cyclopentadienyl ... 

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