Abstract
Acting as a bridge between the heterogeneous and homogeneous realms, the use of discrete, well-defined, solid-state organometallic complexes for synthesis and catalysis is a remarkably undeveloped field. Here, we present a review of this topic, focusing on describing the key transformations that can be observed at a transition-metal centre, as well as the use of well-defined organometallic complexes in the solid state as catalysts. There is a particular focus upon gas–solid reactivity/catalysis and single-crystal-to-single-crystal transformations.
Highlights
Organometallic chemistry, rigorously defined by the chemical synthesis and reactivity of molecules with metal–carbon bonds, is a vibrant area of research with a large variety of practical applications [1]
Organometallic complexes are commonly used as catalysts for the production of commodity chemicals, materials such as polymers, and in fine chemical synthesis and medicinal chemistry discovery [1,2]
These resulting single-site catalysts bring together the benefits of heterogeneous catalysis with the potential for intimate control over the transformations that the metal–ligand environment promotes in a homogeneous system [15,16]; for example, the high degrees of selectivity and mechanistic control associated with a well-defined metal–ligand environment, while harnessing the particular benefits of a solidstate environment
Summary
Organometallic chemistry, rigorously defined by the chemical synthesis and reactivity of molecules with metal–carbon bonds, is a vibrant area of research with a large variety of practical applications [1]. If using reagents in the gas phase that can penetrate the lattice (i.e. a solid–gas reaction), or when in contact with a solvent that will not dissolve the organometallic species but solvates substrates and products, the active organometallic species can partake in the same processes observed in the solution phase, such as ligand substitution, oxidative addition, reductive elimination and insertion reactions These resulting single-site catalysts bring together the benefits of heterogeneous catalysis (i.e. recyclability and easy removal from the reaction mixture) with the potential for intimate control over the transformations that the metal–ligand environment promotes in a homogeneous system [15,16]; for example, the high degrees of selectivity and mechanistic control associated with a well-defined metal–ligand environment, while harnessing the particular benefits of a solidstate environment. Solid-state reactivity using welldefined single-site organometallic complexes potentially allows for the isolation of otherwise unstable complexes, kinetically trapped in the solid state
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