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Communication Dans Un Congrès Année : 2018

Microporous polymers as highly tunable platform for the heterogenization of molecular catalysts

F. Wisser
  • Fonction : Orateur
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Y. Mohr
  • Fonction : Auteur
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P. Berruyer
  • Fonction : Auteur
E. Quadrelli A.
A. Lesage
  • Fonction : Auteur

Résumé

Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks (MOF) and purely organic microporous polymers are promising candidates. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1] Here we present series of heterogeneous catalysts based on MOFs and microporous polymers used as macroligands for heterogenized organometallic complexes.[2] We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity (Scheme 1). This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The general linear trend gives also insight into the contribution of the diffusion limitation inside the porous network of such heterogeneous catalyst. The rational design of heterogenized catalysts can thus be guided by molecular chemistry rules.[2a] The conception of highly efficient heterogeneous catalyst based on porous polymer support and driven by the Hammett parameter of bipyridine-chelating macroligand is demonstrated here for two Rh-catalyzed reactions: The photoreduction of carbon dioxide with turnover frequencies (TOF) up to 28 h-1,[2a] the highest reported for heterogeneous photocatalytic formate production and the transfer hydrogenation reaction of α-aryl ketones with TOFs of up to 3.3 h-1.[2b] References: [1] a) A. Corma, H. García, F. X. Llabrés i Xamena Chem. Rev. 2010, 110, 4606-4655; b) C. Kaes, A. Katz, M; W. Hosseini Chem. Rev. 2000, 100, 3553-3590. [2] a) F. M. Wisser, P. Berruyer, L. Cardenas, Y. Mohr, E. A. Quadrelli, A. Lesage, D. Farrusseng, J. Canivet submitted for publication; b) F. M. Wisser, Y. Mohr, E. A. Quadrelli, D. Farrusseng, J. Canivet ChemCatChem accepted for publication.
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Dates et versions

hal-01744118 , version 1 (27-03-2018)

Identifiants

  • HAL Id : hal-01744118 , version 1

Citer

F. Wisser, Y. Mohr, P. Berruyer, L. Cardenas, E. Quadrelli A., et al.. Microporous polymers as highly tunable platform for the heterogenization of molecular catalysts. 1st GFZ International Conference / 34ème congrès du GFZ, Mar 2018, Cabourg, France. ⟨hal-01744118⟩
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