Structures and Ligand Exchange of N-Confused Porphyrin Dimer Complexes with Group 12 Metals

Hiroyuki Furuta, Tatsuki Morimoto, Atsuhiro Osuka

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    43 Citations (Scopus)

    Abstract

    N-confused 5,20-diphenylporphyrin (NCDPP, 1) formed 2:2 dimer complexes with group 12 metals both in the solid state and in solution. X-ray single-crystal analyses of the Zn(II) and Cd(II) complexes (7, 8) revealed that each metal ion is coordinated with three inner core nitrogens and a peripheral nitrogen of the other NCDPP in the pair. In the 1H NMR spectra of 7, 8, and the Hg(II) complex (9), the outer α-H signals of the confused pyrrole ring appeared in the upfield region at 2.57, 3.44, and 3.60 ppm, respectively, due to the ring current effect by the coordinated porphyrins. In the case of the Cd(II) and Hg(II) complexes (8, 9), additional magnetic couplings with the metal nuclei of the partner rings were observed. The equilibrium constants (K) of the monomer exchange reaction at 25 °C were determined to be 2.5, 1.3, and 0.6 for the (Zn-Cd), (Cd-Hg), and (Zn-Hg) heterodimer complexes, respectively, from the 1H NMR spectra of a solution containing two different dimers. Furthermore, a metal-transfer reaction from a Zn(II) NCP dimer complex to the free base porphyrin was demonstrated.

    Original languageEnglish
    Pages (from-to)1618-1624
    Number of pages7
    JournalInorganic chemistry
    Volume43
    Issue number5
    DOIs
    Publication statusPublished - Mar 8 2004

    All Science Journal Classification (ASJC) codes

    • Physical and Theoretical Chemistry
    • Inorganic Chemistry

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