Chapter 9: Solid/Gas Reactivity of Organometallic Species in Confined Spaces

This chapter considers the chemistry of organometallic compounds in confined spaces in the solid-state. When organometallic species are confined in the solid-state, they are exposed to the constraints of the host framework that influences their stability and reactivity. These conditions provide an extraordinary microenvironment in the solid-state that allows reactivity that often cannot be reproduced in the bulk solvent. Here, we describe selected examples of solid/gas reactivity of transition metal complexes in the solid-state with the focus on describing single-crystal-to-single-crystal transformations of cationic organometallic species hosted in non-covalent anionic frameworks. We provide a general overview on the supramolecular features that can be observed at organometallic guest–host aggregates in the solid-state, with special emphasis on analysing the hydrogen and halogen bonding networks of the microenvironment and gas transport through the crystal structures. We also detail the solid/gas reactivity and catalysis (ligand exchange, alkane dehydrogenation, alkene isomerisation) that can be observed at the confined organometallic species in the solid-state.