4.8 Review

Peroxides in metal complex catalysis

Journal

COORDINATION CHEMISTRY REVIEWS
Volume 437, Issue -, Pages -

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.ccr.2021.213859

Keywords

Peroxides; Metal-peroxy/peroxo complexes; Catalysis; Synthesis

Funding

  1. Fundacao para a Ciencia e Tecnologia (FCT) of Centro de Quimica Estrutural
  2. FCT [DL 57/2016, L 57/2017]
  3. Instituto Superior Tecnico [ISTID/85/2018, IST-ID/110/2018]
  4. RUDN University Strategic Academic Leadership Program
  5. National Natural Science Foundation of China [21261002]
  6. Baku State University, Azerbaijan

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Peroxides are important chemicals with various applications in medicine, industry, and environmental protection. Metal-peroxy/peroxo complexes have specific biological, catalytical, and functional properties and can be used for selective functionalization of organic substrates. The cooperation of metal complexes with peroxides can lead to high-performance multifunctional catalytic systems.
Peroxides form an important class of chemicals in which two oxygen atoms are linked together by a single covalent bond (R-O-O-R, R=H, SO3K, alkyl, etc.), with a wide range of applications in medicine, industry, environmental protection, etc. The current version of the Cambridge Structural Database reveals more than 1400 structurally characterized metal-peroxy/peroxo complexes with diverse coordination modes having specific biological, catalytical and other functional properties. Both inorganic and organic peroxides are versatile oxidants and extensively used reagents for metal complex catalyzed functionalization of organic compounds. The utilization of peroxides in metal complex catalysis typically requires prior activation of O-O or O-R bonds at a metal centre leading to radical species with a reactivity and lifetime that are dependent on the substituents R and reaction medium (pH, solvent, etc.). In fact, the cooperation of a metal centre (coordination) with a peroxide can lead to a multifunctional catalytic system having a high performance towards selective functionalization of organic substrates. This review is intended to focus on the auxiliary/crucial role of peroxides in the transformations of various classes of organic compounds such as alkanes, alkenes, alkynes, aromatics, heterocycles, aldehydes, ketones and alcohols, catalyzed by metal complexes. (C) 2021 Elsevier B.V. All rights reserved.

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