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DFT study on the anionic polymerization of phenyl-substituted [3]dendralene derivatives: reactivities of monomer and chain end carbanion

Polymer Journal volume 54, pages 643–652 (2022)Cite this article

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Abstract

A theoretical study on the anionic polymerization of two phenyl-substituted [3]dendralene derivatives, 2-phenyl[3]dendralene (2-P3D) and (Z)-1-phenyl[3]dendralene (1Z-P3D), was performed using density functional theory (DFT) calculations with ωB97X/6-31 + G(d). The mechanisms of their anionic polymerizations were discussed based on kinetic analysis for chain propagation. In anionic polymerization, 2-P3D and 1Z-P3D were observed to undergo nucleophilic addition exclusively at the C4 position of the [3]dendralene framework, producing 4,1- and 4,6-anions. In the chain propagation of 2-P3D, the 4,1- and 4,6-anions can undergo conjugate addition with comparable activation Gibbs free energies. In contrast, in the chain propagation of 1Z-P3D, the activation Gibbs free energy of the 4,1-addition was much lower than that of the 4,6-addition, indicating that the 4,1-addition was kinetically favorable in the polymerization. These results supported the regioselectivities observed in the anionic polymerizations of 2-P3D and 1Z-P3D. Conformational and molecular orbital analysis showed that the chain end carbanion derived from 1Z-P3D was effectively conjugated with the phenyl substituent; however, that derived from 2-P3D did not. Therefore, the anionic polymerization of phenyl-substituted [3]dendralene derivatives was observed to be strongly influenced by the conjugated structure of the monomer because the position of the phenyl substituent strongly affects the electronic properties of the chain end carbanion.

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Authors and Affiliations

  1. Department of Materials Science and Technology, Nagaoka University of Technology, 1603-1 Kamitomioka, Nagaoka, Niigata, 940-2188, Japan

    Tsukasa Takagi, Tomoyuki Toda, Masamitsu Miya & Katsuhiko Takenaka

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  1. Tsukasa Takagi
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  2. Tomoyuki Toda
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  3. Masamitsu Miya
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  4. Katsuhiko Takenaka
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Correspondence to Katsuhiko Takenaka.

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Takagi, T., Toda, T., Miya, M. et al. DFT study on the anionic polymerization of phenyl-substituted [3]dendralene derivatives: reactivities of monomer and chain end carbanion. Polym J 54, 643–652 (2022). https://doi.org/10.1038/s41428-022-00615-1

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