4.8 Review

The Control of the Coordination Chemistry for the Genesis of Heterogeneous Catalytically Active Sites in Oxidation Reactions

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 45, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202209894

Keywords

Heterogeneous Catalysis; Single-Site Catalysts; Supported Coordination Complexes; Surface Organometallic Chemistry; Sustainable Chemistry

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This review provides an overview of the use and role of coordination complexes as precursors for the generation of hybrid catalysts in oxidation reactions for fine chemical synthesis. The understanding of active site formation in hybrid catalysts is emphasized, and different families of coordination precursors are considered. Each example includes a brief analysis of synthesis, characterization, and catalytic performance. Special attention is given to the chemical environment of the active metal center's first coordination sphere. By integrating advantages of both homogeneous and heterogeneous systems, catalysts obtained through heterogenization, grafting, or anchoring of homogeneous catalysts exhibit enhanced catalytic performance. Deposition of coordination complexes onto preformed supports offers a versatile strategy for designing novel catalysts with tailored and controlled properties.
This Review provides a summary of the use and the role of coordination complexes as precursors for the generation of heterogeneous catalysts for oxidation reactions of interest for fine chemical synthesis. Specific attention is paid to the comprehension of phenomena explaining the formation of active sites in heterogeneous catalysts. Different families of coordination precursors are considered. For each example, a brief critical description of the synthesis, characterization, and catalytic performance is reported. Special attention is paid to the chemical environment of the first coordination sphere of the active metal centre. The catalysts obtained by heterogenization, grafting, or anchoring of homogeneous catalysts can therefore exhibit enhanced catalytic performance by merging advantages of both homogeneous and heterogeneous systems. The deposition of coordination complexes over a preformed support is indeed a conceptually versatile strategy to design novel catalysts with tuned and controlled properties.

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