X-ray snapshot observation of palladium-mediated aromatic bromination in a porous complex

Koki Ikemoto, Yasuhide Inokuma, Kari Rissanen, Makoto Fujita

    Research output: Contribution to journalArticlepeer-review

    54 Citations (Scopus)


    Pd-mediated aromatic bromination is intriguing to synthetic and organometallic chemists due to both its synthetic utility and, more importantly, a proposed mechanism involving an uncommon Pd(IV)/Pd(II) catalytic cycle. Here, we report an X-ray snapshot observation of a Pd reaction center during a Pd-mediated aromatic bromination in a single crystal of a porous coordination network crystalline scaffold. Upon treatment of a single crystal with N-bromosuccinimide, sequential X-ray snapshots revealed that the aryl-Pd(II)-L species embedded in the network pores was converted to the brominated aryl product through a transient aryl-Pd(II)-Br species, which is normally unobservable because of its rapid dimerization into insoluble Pd 2(μ-Br)2 species. Though the reaction pathway may be biased by the crystalline state, the new X-ray snapshot method relies on crystalline flasks to provide important mechanistic insight.

    Original languageEnglish
    Pages (from-to)6892-6895
    Number of pages4
    JournalJournal of the American Chemical Society
    Issue number19
    Publication statusPublished - 2014 May 14

    ASJC Scopus subject areas

    • Catalysis
    • Chemistry(all)
    • Biochemistry
    • Colloid and Surface Chemistry


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