Journal
MACROMOLECULES
Volume 34, Issue 13, Pages 4324-4333Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma001677+
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An investigation of the new synthetic method to synthesize regioregular, head-to-tail coupled poly(3-alkylthiophenes)using magnesium-halogen exchange (Grignard metathesis) called the GRIM method is described. Treatment of 2,5-dibromo-3-alkylthiophenes with a variety of alkyl and vinyl Grignard reagents resulted in two metalated, regiochemical isomers, namely, 2-bromo-3-alkyl-5-bromomagnesiothiophene and 2-bromomagnesio-3-alkyl-5-bromothiophene in an 85:15 ratio. This ratio appears to be independent of reaction time, temperature, and Grignard reagent employed. Introduction of a catalytic amount of Ni(dppp)Cl-2 to this isomeric mixture afforded poly(3-alkylthiophene) that contained greater than 95% KT-HT couplings (typically 98% HT couplings were seen). The high degree of regioregularity found in the polymer can be explained by a combination of kinetic and thermodynamic effects arising from steric and electronic effects found in the catalytic reaction. A series of reaction investigations led to a general explanation of the origin of regioregularity in polythiophene polymerization reactions. These reactions included kinetic studies and competition experiments.
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