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Hangman Salen Platforms Containing Dibenzofuran Scaffolds

Authors

  • Jenny Y. Yang Dr.,

    1. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA 02139 (USA), Fax: (+1) 617-253-7670
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  • Shih-Yuan Liu Dr.,

    1. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA 02139 (USA), Fax: (+1) 617-253-7670
    2. Present address: Department of Chemistry, University of Oregon, 1253 University of Oregon, Eugene, OR 97403-1253 (USA)
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  • Ivan V. Korendovych,

    1. Department of Chemistry, Tufts University, 62 Talbot Avenue, Medford, MA 02155 (USA), Fax: (+1) 617-627-3443
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  • Elena V. Rybak-Akimova Prof.,

    1. Department of Chemistry, Tufts University, 62 Talbot Avenue, Medford, MA 02155 (USA), Fax: (+1) 617-627-3443
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  • Daniel G. Nocera Prof.

    1. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA 02139 (USA), Fax: (+1) 617-253-7670
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Abstract

The synthesis of salen ligands bearing two rigid dibenzofuran spacers functionalized with carboxylic acid and benzoic acid groups completes a series of “Hangman” ligands with the acid functionalities differentially extended across the molecular cleft. Stopped-flow studies show that a high-valent metal oxo intermediate is produced at Hangman platforms when H2O2 is employed as a primary oxidant. The activity of this oxo species in promoting the disproportionation of hydrogen peroxide and olefin epoxidations is discussed in the context of the distance between the acid group and the metal center. The chemistry of the Hangman oxo complexes described here provides a roadmap for water-splitting chemistry.

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