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Reactive N-Protonated Isocyanate Species Stabilized by Bis(μ-hydroxo)divanadium(IV)-Substituted Polyoxometalate

Authors

  • Dr. Kazuhiro Uehara,

    1. Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
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  • Dr. Keisuke Fukaya,

    1. Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
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  • Prof. Dr. Noritaka Mizuno

    Corresponding author
    1. Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
    • Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
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  • We thank Prof. J. Shimoyama (The University of Tokyo) for magnetic susceptibility measurements and his valuable discussion. This work was supported by the global COE program (GCOE) “Chemistry Innovation through Cooperation of Science and Engineering”, the Ministry of Education, Culture, Science, Sports, and Technology of Japan (MEXT) (Japan), and the Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST Program)“ of the Japan Society for the Promotion of Science (JSPS).

Abstract

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O- or N-protonated? The bis(μ-hydroxo)divanadium(IV)-substituted γ-Keggin-type polyoxometalate (see picture, left) (TBA)4[γ-SiVIV2W10O36(μ-OH)4] (TBA=tetra(n-butyl)ammonium) was synthesized and characterized by X-ray crystallography. Its reaction with phenyl isocyanate gave (TBA)4[γ-SiVIV2W10O38(μ-OH)2(PhNHCO)2], which contains two N-protonated phenyl isocyanate species and catalyzes the cyclotrimerization of phenyl isocyanate.

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