Advertisement

One-Pot Multifunctional Catalysis with NNN-Pincer Zr-MOF: Zr Base Catalyzed Condensation with Rh-Catalyzed Hydrogenation

Authors

  • Antonia M. Rasero-Almansa,

    1. Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas, C/Sor Juana Inés de la Cruz, n° 3, 28049 Madrid (Spain), Fax: (+34) 913720623
    Search for more papers by this author
  • Prof. Avelino Corma,

    Corresponding author
    1. Instituto de Tecnología Química, Consejo Superior de Investigaciones Cientificas, Universitat Politècnica de València, Avda. los Naranjos, s/n, 46022 Valencia (Spain)
    • Instituto de Tecnología Química, Consejo Superior de Investigaciones Cientificas, Universitat Politècnica de València, Avda. los Naranjos, s/n, 46022 Valencia (Spain)
    Search for more papers by this author
  • Prof. Marta Iglesias,

    Corresponding author
    1. Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas, C/Sor Juana Inés de la Cruz, n° 3, 28049 Madrid (Spain), Fax: (+34) 913720623
    • Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas, C/Sor Juana Inés de la Cruz, n° 3, 28049 Madrid (Spain), Fax: (+34) 913720623
    Search for more papers by this author
  • Prof. Félix Sánchez

    1. Instituto de Química Orgánica General, Consejo Superior de Investigaciones Cientificas, C/Juan de la Cierva, n° 3, 28006 Madrid (Spain)
    Search for more papers by this author

Abstract

We describe the postsynthetic modification of Zr-based metal organic frameworks (MOFs) containing chiral NNN-pincer ligands based on aminopyridineimines, as well as the subsequent formation of (NNN)-M-Zr-MOF complexes (M=Rh, Ir). With these new multifunctional materials, we performed a cascade of condensation reactions followed by hydrogenation of the resulting double bond. If the condensation reaction occurs between an aldehyde and ethyl nitroacetate, (NNN)–M–Zr-MOF complexes catalyze the one-pot synthesis of nitroalkenes, in which ZrIV Lewis sites play a role similar to that of the generally used TiIV in homogeneous catalysis. These multifunctional hybrid catalysts retain their crystalline framework even after the reaction, and they were isolated easily from the reaction mixture through filtration and reused several times without a significant degradation in activity. Moreover, there was no contribution from leached active species and conversion was possible only in the presence of the solid catalyst.

Ancillary