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Kumada-Tamao coupling polymerization of 6-bromo-3-chloromagnesio-2-(3-(2-methoxyethoxy)propyl)pyridine 1 with a Ni catalyst and Suzuki-Miyaura coupling polymerization of boronic ester monomer 2, which has the same substituted pyridine structure, with tBu3PPd( o-tolyl)Br were investigated for the synthesis of a well-defined n-type π-conjugated polymer. We first carried out a model reaction of 2,5-dibromopyridine with 0.5 equivalent of phenylmagnesium chloride in the presence of Ni(dppp)Cl2 and then observed exclusive formation of 2,5-diphenylpyridine, indicating that successive coupling reaction took place via intramolecular transfer of Ni(0) catalyst on the pyridine ring. Then, we examined the Kumada-Tamao polymerization of 1 and found that it proceeded homogeneously to afford soluble, regioregular head-to-tail poly(pyridine-2,5-diyl), poly(3-(2-(2-(methoxyethoxy)propyl)pyridine) (PMEPPy). However, the molecular weight distribution of the polymers obtained with several Ni and Pd catalysts was very broad, and the matrix-assisted laser desorption ionization time-of-flight mass spectra showed that the polymer had Br/Br and Br/H end groups, implying that the catalyst-transfer polymerization is accompanied with disproportionation. Suzuki-Miyaura polymerization of 2 with tBu3PPd( o-tolyl)Br also afforded PMEPPy with a broad molecular weight distribution, and the tolyl/tolyl-ended polymer was a major product, again indicating the occurrence of disproportionation. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 [ABSTRACT FROM AUTHOR]

We studied the mechanism of the chain-growth polymerization of 2-bromo-5-chloromagnesio-3-hexylthiophene (1) with Ni(dppp)Cl2 [dppp = 1 ,3-bis(diphenylphosphino)propane], in which head-to-tail poly(3-hexylthiophene) (HT-P3HT) with a low polydispersity is obtained and the Mn is controlled by the feed ratio of the monomer to the Ni catalyst. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectra showed that the HT-P3HT uniformly had a hydrogen atom at one end of each molecule and a bromine atom at the other. The reaction of the polymer with aryl Grignard reagent gave HT-P3HT with aryl groups at both ends, which indicates that the H-end was derived from the propagating Ni complex. The degree of polymerization and the absolute molecular weight of the polymer could be evaluated from the 1H NMR spectra of the Ar/Ar-ended HT-P3HT, and it was found that one Ni catalyst molecule forms one polymer chain. Furthermore, by reaction of 1 with 50 mol % Ni(dppp)Cl2, the chain initiator was found to be a bithiophene-Ni complex, formed by a coupling reaction of 1 followed by insertion of the Ni(0) catalyst into the C-Br bond of the dimer. On the basis of these results, we propose that this chain-growth polymerization involves the coupling reaction of 1 with the polymer via the Ni catalyst, which is transferred intramolecularly to the terminal C-Br bond of the elongated molecule. We call this mechanism "catalyst- transfer polycondensa tiorP. [ABSTRACT FROM AUTHOR]

The article focuses on the organometallic polycondensation as a reliable method for the synthesis of polymers. The molecular weight and polydispersity of the polymers are not well-controlled due to the step-growth polymerization nature of polycondensation. The catalyst-transfer Suzuki-Miyaura coupling polymerization is investigated and it was found that dioxaborolane, with a catalytic amount of 2 through the coupling reaction, showed a narrow molecular weight distribution.

Acetalization of aromatic aldehydes 1 with bis(trimethylsilyl ether)s 2 or 4 in the presence of a Lewis-acid catalyst was investigated. Under the optimized conditions, this reaction initially gave a mixture of oligomers, which converged to a [2 + 2] macrocycle in high yield via reversible transacetalation. [ABSTRACT FROM AUTHOR]

The article examines the catalyst transfer of conductive polymers with controlled molecular weight and low polydispersity. In one study, the polycondensation of a Grignard thiophene monomer with Ni-Cl2 as catalysts would proceed into a chain-growth polymerization mechanism. A monomer addition experiment was conducted to determine the chain-growth nature of the polymerization.