Abstract

The design of highly active metal nanoparticles to be employed as efficient heterogeneous catalysts is a key tool for the construction of complex organic molecules and the minimization of their environmental costs. The formation of novel C–N bonds via C–H activation is an effective atom-economical strategy to access high value materials in pharmaceuticals, polymers, and natural product production. In this contribution, the literature of the last ten years on the use of metal nanoparticles in the processes involving direct C–N bond formation will be discussed. Where possible, a discussion on the role and influence of the support used for the immobilization and/or the metal chosen is reported. Particular attention was given to the description of the experiments performed to elucidate the active mechanism.

Highlights

  • IntroductionHomogeneous metal complexes are highly efficient in C–H activation reactions [18,19,20,21,22,23,24,25,26], their difficult reusability and the inevitable waste produced from their separation from reaction products constitutes an important limitation for their actual use

  • The precious metals, generally used as homogenous catalytic systems, could possibly be replaced with more convenient heterogeneous systems that allow for an easy separation of the catalyst from the reaction mixture, the reuse of the catalytic system and a minimization of product metal contamination

  • We focused on the employment of metal nanoparticles as heterogeneous catalytic systems

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Summary

Introduction

Homogeneous metal complexes are highly efficient in C–H activation reactions [18,19,20,21,22,23,24,25,26], their difficult reusability and the inevitable waste produced from their separation from reaction products constitutes an important limitation for their actual use To overcome these issues and improve the sustainability of. When MNPs are used in catalysis, the catalytic cycle can take place directly on the nanoparticle surfaces (heterogeneous mechanism) or it can be promoted by some soluble species released in solution (homogeneous mechanism) In the latter case, effective nanocatalysts are of major interest if the metallic active species returns to the surface at the end of the catalytic cycle, defining a “release and catch” mechanism [54,55]. These data generally highlight the importance and the role of the support chosen and/or the conditions selected for the synthesis of MNPs to obtain high catalytic efficiencies

C–H Amidation
C–H Amination
C–N Bond Formation in the Synthesis of Heterocycles
Findings
Conclusions and Future Outlooks
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