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Reactivity and Selectivity of Heterogenized Homogeneous Catalysts: Insights from Molecular Simulations

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Heterogenized Homogeneous Catalysts for Fine Chemicals Production

Part of the book series: Catalysis by Metal Complexes ((CMCO,volume 33))

Abstract

Immobilized metal complexes on nanoporous materials have recently been proposed as a novel class of heterogeneous enantioselective catalyst for epoxidation of unfunctionalized olefins as well as hydrogenation, alkylation, and nitroaldol reactions. The porous hosted materials affect catalytic performance due to a cooperative interaction among the nanoporous solid, immobilizing linker, and metal complex asymmetry. The effects of mesoporous materials and immobilizing agents on chiral catalysis are not well understood, however, the catalysts confined in nanopores show comparable or even higher conversions and enantioselectivity compared to their homogeneous counterparts. This chapter highlights major scientific problems for fundamental understanding and design of heterogenized homogeneous catalysts. It describes in detail the pivotal role of a sound framework in physical theory and molecular modeling in systematic efforts towards better materials and catalytic performance optimization. The common threads of the various topics addressed is the wide range of scales that has to be considered in establishing relations between structure, physicochemical properties, and catalytic performance. Physical theory and modeling employ a variety of methods, encompassing ab-initio calculations, molecular simulations, and the continuum model of transport and reaction in nanoporous materials. We particularly describe how molecular simulations can be used to investigate the origin of enantioselectivity of an anchored metal complex in nanoporous materials. These studies provide new insights into the steric effects that relate to choices of substrate and linker and to the interplay with mesopore confinement. We also bring detailed example of employing molecular simulations to unravel the catalytic properties of metallomacrocyclics for the electrochemical reduction of molecular oxygen in aqueous media. We rationalize the importance of immobilization and show how it relates to the steric communication between the substrate and the metal complex. These fundamental concepts are important for the interpretation of the enantioselectivity of immobilized organometallic catalysts in nanoporous materials.

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Authors and Affiliations

  1. National Research Council of Canada, Institute for Fuel Cell Innovation, 4250 Wesbrook Mall, V6T 1W5, Vancouver, BC, Canada

    Kourosh Malek

  2. Department of Chemistry, Simon Fraser University, 8888 University Drive, V5A 1S6, Burnaby, BC, Canada

    Kourosh Malek

  3. Schuit Institute of Catalysis, ST/SKA, Eindhoven University of Technology, Eindhoven, The Netherlands

    Rutger A. Van Santen

Authors
  1. Kourosh Malek
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  2. Rutger A. Van Santen
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Correspondence to Kourosh Malek .

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Editors and Affiliations

  1. Istituto di Chimica dei Composti, Organometallici (ICCOM), CNR Firenze, Via Madonna del Piano 10, Sesto Fiorentino, 50019, Firenze, Italy

    Pierluigi Barbaro

  2. Istituto di Chimica dei Composti, Organometallici (ICCOM), CNR Firenze, Via Madonna del Piano 10, Sesto Fiorentino, 50019, Firenze, Italy

    Francesca Liguori

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Malek, K., Van Santen, R.A. (2010). Reactivity and Selectivity of Heterogenized Homogeneous Catalysts: Insights from Molecular Simulations. In: Barbaro, P., Liguori, F. (eds) Heterogenized Homogeneous Catalysts for Fine Chemicals Production. Catalysis by Metal Complexes, vol 33. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-3696-4_12

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