Palladium Catalysts Supported on Mesoporous Molecular Sieves Bearing Nitrogen Donor Groups: Preparation and Use in Heck and Suzuki C[BOND]C Bond-Forming Reactions

Authors

  • Jan Demel,

    1. Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 12840 Prague 2 (Czech Republic), Fax: (+42) 0221 951 253
    2. J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic v.v.i, Dolejškova 3, 18223 Prague 8 (Czech Republic), Fax: (+42) 0286 582 307
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  • Martin Lamač Dr.,

    1. Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 12840 Prague 2 (Czech Republic), Fax: (+42) 0221 951 253
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  • Jiří Čejka Prof.,

    1. J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic v.v.i, Dolejškova 3, 18223 Prague 8 (Czech Republic), Fax: (+42) 0286 582 307
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  • Petr Štěpnička Prof.

    1. Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 12840 Prague 2 (Czech Republic), Fax: (+42) 0221 951 253
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Abstract

Best pals: Catalysts prepared from palladium(II) acetate and SBA-15-type mesoporous molecular sieves bearing [TRIPLE BOND]SiCH2CH2CH2NHCH2CH2NEt2 groups at the surface efficiently catalyze the Suzuki and Heck reactions. In the former reaction, the highly metalated catalysts prove to be more efficient while the influence of the metal loading in the latter is more complex: A catalyst with a very low metal loading is particularly attractive, being highly active, recyclable, and applicable as a bifunctional catalyst.

original image

A series of supported catalysts is prepared by treatment of SBA-15-type mesoporous molecular sieve bearing [TRIPLE BOND]SiCH2CH2CH2NHCH2CH2NEt2 groups with palladium(II) acetate. These catalysts are studied in Suzuki biaryl couplings and in Heck reactions to establish the influence of metal loading and innocent surface modifications (trimethylsilylation). The Suzuki reaction proceeded efficiently with model and practically relevant substrates; the catalyst performance increasing with an increasing degree of metalation (decreasing N/Pd ratio). Catalyst poisoning tests revealed that the reaction takes place in the liquid phase with the catalyst serving as a reservoir of active metal species and also as a stabilizing support once the reaction is performed. In the Heck reactions, on the other hand, the catalyst performance strongly changed with the reaction temperature and with the N/Pd ratio. The material with the lowest metal loading (0.01 mmol palladium per gram of material, N/Pd ratio ca. 100:1) proved particularly attractive in the Heck coupling, being highly active at elevated temperatures, recyclable, and capable of acting as a bifunctional catalyst (i.e., functioning without any external base.

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