Rh chemistry through the eyes of theory

Abstract

We discuss the properties of Rh and its compounds from a theoretical chemistry perspective. Like its neighbors in the platinum metal group, this element exhibits a remarkable spectrum of catalytic activity both as an elemental metal and as the central ion of transition metal complexes. This property is reflected in a comparatively weak chemical bond dominated by d–p interactions, varying oxidation states and a highly flexible coordination shell. In turn, theoretical methods and their generalization as empirical concepts have to be able to deal with a multitude of binding situations and the strong electron–electron interaction within the Rh valence orbitals. Whereas density functional theory has greatly enhanced the computational accessibility of Rh compounds, quantitative models of catalytic cycles require a more explicit treatment of static electron correlation, such as integrated density functional‐coupled cluster schemes. WIREs Comput Mol Sci 2016, 6:311–320. doi: 10.1002/wcms.1250This article is categorized under: Structure and Mechanism > Molecular Structures Structure and Mechanism > Reaction Mechanisms and Catalysis