Influence of the Boron Moiety and Water on Suzuki–Miyaura Catalyst‐Transfer Condensation Polymerization

  • Kentaro Kosaka
    Department of Material and Life Chemistry Kanagawa University Rokkakubashi Kanagawa‐ku, Yokohama 221–8686 Japan
  • Tsutomu Yokozawa
    Department of Material and Life Chemistry Kanagawa University Rokkakubashi Kanagawa‐ku, Yokohama 221–8686 Japan
  • Yoshihiro Ohta
    Department of Material and Life Chemistry Kanagawa University Rokkakubashi Kanagawa‐ku, Yokohama 221–8686 Japan

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Published
2014-12-12
Resource Type
journal article
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  • http://onlinelibrary.wiley.com/termsAndConditions#vor
DOI
  • 10.1002/marc.201400530
Publisher
Wiley

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<jats:p>Although water promotes Suzuki–Miyaura coupling reaction, it also induces side reactions such as deboronation and dehalogenation. Therefore, Suzuki–Miyaura polymerization of triolborate halothiophene monomer <jats:bold>1</jats:bold> with <jats:italic><jats:sup>t</jats:sup></jats:italic>Bu<jats:sub>3</jats:sub>PPd(<jats:italic>o</jats:italic>‐tolyl)Br (<jats:bold>2</jats:bold>) in dry tetrahydrofuran (THF) is investigated. However, the resultant poly(3‐hexylthiophene) (P3HT) shows a broad molecular weight distribution and uncontrolled polymer ends. Model reactions of a number of boron reagents <jats:bold>3</jats:bold> with 2,5‐dibromothiophene (<jats:bold>4</jats:bold>) in the presence or absence of water indicate that intramolecular transfer of the catalyst is hardly affected by the boron moiety of <jats:bold>3</jats:bold>, whereas it is hindered in the absence of water. Indeed, polymerization of <jats:bold>1</jats:bold> with <jats:bold>2</jats:bold> in H<jats:sub>2</jats:sub>O/THF affords P3HT with a narrower molecular weight distribution and controlled tolyl/H ends, as compared to the reaction in dry THF. <jats:boxed-text content-type="graphic" position="anchor"><jats:graphic xmlns:xlink="http://www.w3.org/1999/xlink" mimetype="image/png" position="anchor" specific-use="enlarged-web-image" xlink:href="graphic/marc201400530-abs-0001-m.png"><jats:alt-text>image</jats:alt-text></jats:graphic></jats:boxed-text></jats:p>

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