<scp>S</scp>uzuki Polycondensation

Sakamoto, Junji; Schlüter, A. Dieter

doi:10.1002/9783527603978.mst0432

Cited by 2 publications

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“…Suzuki–Miyaura cross-coupling is one of the most prominent tools for aryl–aryl or aryl–vinyl bond formation in organic synthesis. , It has also been utilized for the synthesis of polymers then being referred to as Suzuki polycondensation (SPC). , A great variety of polyphenylenes and related polymers have been prepared by SPC in both academia and industry often aiming at applications in electroluminescent devices . In contrast to poly( p -phenylene) (PPP) and its derivatives, poly( m -phenylene) (PMP) has been much less explored.…”

Section: Introductionmentioning

confidence: 99%

Suzuki Polycondensation toward High Molecular Weight Poly(m-phenylene)s: Mechanistic Insights and End-Functionalization

et al. 2012

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Synthesis of a poly(m-phenylene) by Suzuki polycondensation (SPC) using an AB-type m-phenylene monomer is reported (A and B refer to bromo and boron functional groups, respectively). Despite the attempted high molecular weight products, SPC under the conventional conditions using Pd[P(p-Tol)3]3 as catalyst gave rise to oligomeric products only. They comprise cycles and several series of open-chain poly(m-phenylene)s with various end group patterns. These patterns were caused by side reactions such as ligand scrambling. Buchwald’s SPhos ligand was therefore alternatively employed for high turnover catalysis to accelerate SPC over such detrimental side reactions. This modification indeed led to the formation of high molecular weight products ∼40 kDa (DP ∼ 210), while oligomeric cyclic products still remained prominent. Cycle formation could, however, drastically be reduced by slow monomer addition. SPC was also performed in the presence of an excess monofunctional compound, R–A or R–B. The molecular weights of the products were found to be sensitive to the presence of R–B but not so much to R–A. This suggests a chain-growth-like mechanism as previously reported by Yokozawa et al. The modified SPC protocol was also used to demonstrate an efficient end-functionalization of the SPC products at both A and B termini with distinct chemical moieties. This revealed that the chain directionality expected from the AB monomer was largely retained when Pd(dba)2 was used as palladium source for the SPC catalyst but not as for Pd(OAc)2. This is presumably due to involvement of the homocoupling between phenyl boronates leading to reduction of Pd(II).

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Section: Introductionmentioning

confidence: 99%

Suzuki Polycondensation toward High Molecular Weight Poly(m-phenylene)s: Mechanistic Insights and End-Functionalization

et al. 2012

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“…INTRODUCTION Direct arylation polymerization (DArP) for the synthesis of conjugated polymers has emerged recently as an alternative to traditional methods of transition metal catalyzed polymerization, such as Stille, 1 Suzuki, 2,3 Negishi, 4 and Kumada 5 polymerizations with Stille polymerization being especially popular since nearly all the top performing conjugated polymers for the organic photovoltaics (OPV) application are made by Stille polymerization. In contrast with these methods, which require functionalization of monomers with organotin (Stille), organoboron (Suzuki), organozinc (Negishi), or organomagnesium (Kumada) groups, DArP as a C-H activation method allows polymerization of unfunctionalized monomers as illustrated in Figure 1.…”

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Optimization of direct arylation polymerization (DArP) through the identification and control of defects in polymer structure

Rudenko

Thompson

2014

J. Polym. Sci. Part A: Polym. Chem.

190

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As a newly emerged protocol for the synthesis of conjugated polymers, direct arylation polymerization (DArP) is an environmentally friendly and cost-effective alternative to traditional methods of polymerization. DArP efficiently yields conjugated polymers with high yield and high molecular weight. However, DArP is also known to produce defects in polymer chemical structure. Together with molecular weight and polydispersity, these defects are considered to be important parameters of polymer structure and they have a strong impact on optical, electronic and thermal properties of conjugated polymers. The four major classes of conjugated polymer defects inherent for DArP have been identified: homocoupling regiodefects, branching defects, end group defects, and residual metal defects. To have a precise control over the polymer properties, it is important to understand what causes the defects to form during the polymerization process and be able to control their content. Here within the scope of current literature, we discuss in detail the definition and origin of all these defects, their influence on polymer properties and effective means to control the defects through fine tuning of the DArP reaction parameters.

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Suzuki Polycondensation

Abstract: The sections in this article are Introduction General Remarks How to Perform SPC , and Aspects of Characterization Monomer Purity and Stoichiometry Polymerization and End‐Capping Purification and Side Reactions Molar Mass… Show more

Cited by 2 publications

References 220 publications

Suzuki Polycondensation toward High Molecular Weight Poly(m-phenylene)s: Mechanistic Insights and End-Functionalization

Suzuki Polycondensation toward High Molecular Weight Poly(m-phenylene)s: Mechanistic Insights and End-Functionalization

Optimization of direct arylation polymerization (DArP) through the identification and control of defects in polymer structure

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