Reactivity of Ruthenium(II) and Copper(I) Complexes that Possess Anionic Heteroatomic Ligands: Synthetic Exploitation of Nucleophilicity and Basicity of Amido, Hydroxo, Alkoxo, and Aryloxo Ligands for the Activation of Substrates that Possess Polar Bonds as well as Nonpolar C–H and H–H Bonds (Eur. J. Inorg. Chem. 9/2007)

Abstract

AbstractThe cover picture shows the disruption of amido‐ and alkoxo‐to‐metal π‐donation because of a filled dπ manifold, which occurs for metal centers in low oxidation states and which renders the anionic amido, alkoxo and related ligands highly reactive. The low oxidation states decrease the predilection toward metal‐center reduction and, as a result, tend to promote “even‐electron” chemistry over odd‐electron radical chemistry that is based on net single‐electron reduction of the metal. For RuII and CuI complexes, evidence for the enhanced reactivity of the heteroatomic ligands is derived from acid/base reactions as well as from nucleophilic additions. The combination of a Lewis acid metal center and a basic/nucleophilic heteroatomic ligand (amido, hydroxo, alkoxo, etc.) can be exploited for the activation of substrates that possess polar and nonpolar bonds, for example for metal‐mediated C–H activation and for catalytic hydroamination and hydroalkoxylation of activated olefins. Details are presented in the Microreview by T. B. Gunnoe on p. 1185 ff.