Transition metal catalysis in confined spaces

Stefan H a M Leenders (1) , Rafael Gramage-Doria (1) , Bas de Bruin (1) , Joost N H Reek (1)

1 van ‘t Hoff Institute for Molecular Sciences

Transition metal catalysis in confi ned spaces This review discusses diff erent approaches to confi ne or 'cage' transition metal catalysts and demonstrates that the confi nement leads to control of reactivity and selectivity beyond that of free metal complexes. Registered charity number: 207890 www.rsc.org/chemsocrev This journal is Transition metal catalysis plays an important role in both industry and in academia where selectivity, activity and stability are crucial parameters to control. Next to changing the structure of the ligand, introducing a confined space as a second coordination sphere around a metal catalyst has recently been shown to be a viable method to induce new selectivity and activity in transition metal catalysis. In this review we focus on supramolecular strategies to encapsulate transition metal complexes with the aim of controlling the selectivity via the second coordination sphere. As we will discuss, catalyst confinement can result in selective processes that are impossible or difficult to achieve by traditional methods. We will describe the template-ligand approach as well as the host–guest approach to arrive at such supramolecular systems and discuss how the performance of the catalyst is enhanced by confining it in a molecular container.

Domains: Chemical Sciences; Catalysis

Stefan H a M Leenders, Rafael Gramage-Doria, Bas de Bruin, Joost N H Reek. Transition metal catalysis in confined spaces. Chemical Society Reviews, 2015, 44, pp.433-448. ⟨10.1039/c4cs00192c⟩. ⟨hal-01472875⟩