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Halogen effects on phenylethynyl palladium(II) complexes for living polymerization of isocyanides: a combined experimental and computational investigation

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Abstract

Phenylethynyl palladium(II) complexes have proven to be effective catalysts for coordination polymerization of isocyanides. In this work, two new phenylethynyl palladium(II) initiators bearing bromide (1b) and iodide (1c) were synthesized and applied for living polymerization of aryl and alkyl isocyanides. The coordinated halogen anions can significantly influence the kinetics of polymerization, with the observed order of reaction rates being 1c (I)>1b (Br)>1a (Cl). Impressively, 1c not only accelerates the reaction rate in both the initiation stage and propagation stage, but also can polymerize less active monomers that cannot be reacted by 1a. DFT calculations were then employed to understand the detailed mechanism and the halogen effects in this insertion polymerization process.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21771049, 21622402), the Fundamental Research Funds for the Central Universities, the National Thousand Young Talents Program, the Jiangsu Specially-Appointed Professor Plan, and the Natural Science Foundation of Jiangsu Province (BK20170631).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Anhui Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei University of Technology, Hefei, 230009, China

    Yaqi Wang, Zhiqiang Jiang, Fang Liu, Yuanyuan Zhu & Zongquan Wu

  2. State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China

    Yu Chen, Fang Liu & Yong Liang

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  1. Yaqi Wang
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  2. Yu Chen
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  4. Fang Liu
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  5. Fang Liu
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  6. Yuanyuan Zhu
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  7. Yong Liang
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Correspondence to Yuanyuan Zhu, Yong Liang or Zongquan Wu.

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11426_2018_9415_MOESM2_ESM.pdf

Halogen Effects on Phenylethynyl Palladium(II) Complexes for Living Polymerization of Isocyanides: A Combined Experimental and Computational Investigation

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Wang, Y., Chen, Y., Jiang, Z. et al. Halogen effects on phenylethynyl palladium(II) complexes for living polymerization of isocyanides: a combined experimental and computational investigation. Sci. China Chem. 62, 491–499 (2019). https://doi.org/10.1007/s11426-018-9415-8

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  • DOI: https://doi.org/10.1007/s11426-018-9415-8

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