Di-and trinuclear Zn2+ complexes of calyx

Roberta Cacciapaglia, Alessandro Casnati, Luigi Mandolini, David Reinhoudt

    Research output: Contribution to journalArticleAcademicpeer-review

    48 Citations (Scopus)

    Abstract

    The calix[4]arene scaffold, blocked in the cone conformation by proper alkylation of the lower rim hydroxyls, was used as a convenient molecular platform for the design of bi- and trimetallic Zn2+ catalysts. The catalytic activity of the Zn2+ complexes of calix[4]arenes decorated at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with 2,6-bis[(dimethylamino)methyl]pyridine units were investigated in the cleavage of ester 6 and of the RNA model compound HPNP. High rate enhancements, up to 4 orders of magnitude, were observed in a number of catalyst−substrate combinations. Interestingly the order of catalytic efficiency among regioisomeric dinuclear complexes in the cleavage of ester 6 is 1,2-vicinal 1,3-distal, but it is reversed in the reaction of HPNP. The higher efficiency of trinuclear compared to dinuclear complexes provides an indication of the cooperation of three Zn2+ ions in the catalytic mechanism.
    Original languageUndefined
    Pages (from-to)1-7
    JournalJournal of organic chemistry
    Volume70
    Issue number2
    DOIs
    Publication statusPublished - 2005

    Keywords

    • IR-52893
    • METIS-224854

    Cite this

    Cacciapaglia, Roberta ; Casnati, Alessandro ; Mandolini, Luigi ; Reinhoudt, David. / Di-and trinuclear Zn2+ complexes of calyx. In: Journal of organic chemistry. 2005 ; Vol. 70, No. 2. pp. 1-7.
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    title = "Di-and trinuclear Zn2+ complexes of calyx",
    abstract = "The calix[4]arene scaffold, blocked in the cone conformation by proper alkylation of the lower rim hydroxyls, was used as a convenient molecular platform for the design of bi- and trimetallic Zn2+ catalysts. The catalytic activity of the Zn2+ complexes of calix[4]arenes decorated at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with 2,6-bis[(dimethylamino)methyl]pyridine units were investigated in the cleavage of ester 6 and of the RNA model compound HPNP. High rate enhancements, up to 4 orders of magnitude, were observed in a number of catalyst−substrate combinations. Interestingly the order of catalytic efficiency among regioisomeric dinuclear complexes in the cleavage of ester 6 is 1,2-vicinal 1,3-distal, but it is reversed in the reaction of HPNP. The higher efficiency of trinuclear compared to dinuclear complexes provides an indication of the cooperation of three Zn2+ ions in the catalytic mechanism.",
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    author = "Roberta Cacciapaglia and Alessandro Casnati and Luigi Mandolini and David Reinhoudt",
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    journal = "Journal of organic chemistry",
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    Cacciapaglia, R, Casnati, A, Mandolini, L & Reinhoudt, D 2005, 'Di-and trinuclear Zn2+ complexes of calyx', Journal of organic chemistry, vol. 70, no. 2, pp. 1-7. https://doi.org/10.1021/jo0487350

    Di-and trinuclear Zn2+ complexes of calyx. / Cacciapaglia, Roberta; Casnati, Alessandro; Mandolini, Luigi; Reinhoudt, David.

    In: Journal of organic chemistry, Vol. 70, No. 2, 2005, p. 1-7.

    Research output: Contribution to journalArticleAcademicpeer-review

    TY - JOUR

    T1 - Di-and trinuclear Zn2+ complexes of calyx

    AU - Cacciapaglia, Roberta

    AU - Casnati, Alessandro

    AU - Mandolini, Luigi

    AU - Reinhoudt, David

    PY - 2005

    Y1 - 2005

    N2 - The calix[4]arene scaffold, blocked in the cone conformation by proper alkylation of the lower rim hydroxyls, was used as a convenient molecular platform for the design of bi- and trimetallic Zn2+ catalysts. The catalytic activity of the Zn2+ complexes of calix[4]arenes decorated at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with 2,6-bis[(dimethylamino)methyl]pyridine units were investigated in the cleavage of ester 6 and of the RNA model compound HPNP. High rate enhancements, up to 4 orders of magnitude, were observed in a number of catalyst−substrate combinations. Interestingly the order of catalytic efficiency among regioisomeric dinuclear complexes in the cleavage of ester 6 is 1,2-vicinal 1,3-distal, but it is reversed in the reaction of HPNP. The higher efficiency of trinuclear compared to dinuclear complexes provides an indication of the cooperation of three Zn2+ ions in the catalytic mechanism.

    AB - The calix[4]arene scaffold, blocked in the cone conformation by proper alkylation of the lower rim hydroxyls, was used as a convenient molecular platform for the design of bi- and trimetallic Zn2+ catalysts. The catalytic activity of the Zn2+ complexes of calix[4]arenes decorated at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with 2,6-bis[(dimethylamino)methyl]pyridine units were investigated in the cleavage of ester 6 and of the RNA model compound HPNP. High rate enhancements, up to 4 orders of magnitude, were observed in a number of catalyst−substrate combinations. Interestingly the order of catalytic efficiency among regioisomeric dinuclear complexes in the cleavage of ester 6 is 1,2-vicinal 1,3-distal, but it is reversed in the reaction of HPNP. The higher efficiency of trinuclear compared to dinuclear complexes provides an indication of the cooperation of three Zn2+ ions in the catalytic mechanism.

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    KW - METIS-224854

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