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Iodo-Bridged Transition States; New Mechanistic Pathways for Base-Catalyzed Halogen Dance

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Abstract

First reported by Joseph Bunnet et al., base-catalyzed halogen dance reaction has puzzled chemists for decades, to come up with new ideas regarding the mechanism of this chemical reaction. A series of deprotonation followed by fast metal-halogen exchanges are among the most recent mechanisms reported so far. Using density functional theory, DFT, computations and focused on the Bunnet type isomerization halogen dance reactions of iodobenzene derivatives, iodo-bridged transition state, TS, are proposed. The new TS is then used to lay out 8 possible isomerization and 18 possible disproportionation paths. The possible mechanistic pathways are then carefully analyzed based on TS’s energy and protonation/deprotonation steps to find the most suitable pathways. These mechanistic pathways, sketch a comprehensive pattern for base-catalyzed halogen dance. There is still a lot to study in the chemistry of poly halogenated aryls.

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Authors and Affiliations

  1. Department of Chemistry, University of Illinois Urbana-Champaign, Urbana, IL, 61820, USA

    Nader Sakhaee

  2. Islamic Azad University, Mashhad Branch, Mashhad, Iran

    Sahar Sakhaee

  3. International Center for Materials Nanoarchitechtonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan

    Esmail Doustkhah

  4. Department of Chemistry, Tarbiat Modarres University, P.O. Box, 14115-175, Tehran, Iran

    Akbar mobaraki

  5. Department of Chemistry, Kharazmi University, Tehran, Iran

    Ahmad Takallou

  6. Mashhad University of Medical Sciences, Mashhad, Iran

    Mohammad Hossein Sakhaee

Authors
  1. Nader Sakhaee
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  2. Sahar Sakhaee
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  4. Akbar mobaraki
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Correspondence to Nader Sakhaee.

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Sakhaee, N., Sakhaee, S., Doustkhah, E. et al. Iodo-Bridged Transition States; New Mechanistic Pathways for Base-Catalyzed Halogen Dance. Chemistry Africa 4, 37–49 (2021). https://doi.org/10.1007/s42250-020-00197-6

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