Ménage-à-trois: single-atom catalysis, mass spectrometry, and computational chemistry

There is no author summary for this article yet. Authors can add summaries to their articles on ScienceOpen to make them more accessible to a non-specialist audience.

Abstract

Genuine, single-atom catalysis can be realized in the gas phase and probed by mass spectrometry combined with computational chemistry.

Abstract

This review provides an overview and an update on how single-atom catalysis can be achieved at a strictly molecular level by performing well-designed gas-phase experiments complemented by quantum chemical calculations. Examples discussed include mechanistic aspects of (i) metal-mediated carbon–carbon bond formation (coupling of methane), (ii) the room temperature oxygen-atom transfer in the redox couple N ₂O/CO, and (iii) the selective oxidation of inert substrates like H ₂ or CH ₄ by mass-selected metal oxides. While this novel approach, in principle, never accounts for many details of processes occurring in solution or on a surface, it has proved extremely useful in providing a conceptual framework.

Related collections

Most cited references 143

Record: found
Abstract: found
Article: not found

Catalysis of Radical Reactions: A Radical Chemistry Perspective

Armido Studer, Dennis Curran (2016)

The area of catalysis of radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms of catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most radical reactions have innate chains which form products without any catalyst. How do we know if a species added in "catalytic amounts" is a catalyst, an initiator, or something else? Herein we critically address both catalyst-free and catalytic radical reactions through the lens of radical chemistry. Basic principles of kinetics and thermodynamics are used to address problems of initiation, propagation, and inhibition of radical chains. The catalysis of radical reactions differs from other areas of catalysis. Whereas efficient innate chain reactions are difficult to catalyze because individual steps are fast, both inefficient chain processes and non-chain processes afford diverse opportunities for catalysis, as illustrated with selected examples.