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

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AbstractThe preparation and reactivity of late transition‐metal complexes in low oxidation states with nondative‐heteroatomic ligands (e.g., amido, hydroxo, alkoxo, and aryloxo ligands) are described. For such complexes the disruption of ligand‐to‐metal π‐donation because of a filled dπ manifold can enhance the nucleophilic and/or basic reactivity at the nondative‐heteroatomic ligand relative to transition‐metal complexes in high oxidation states. The chemistry of five‐ and six‐coordinate Ru complexes with amido, hydroxo, methoxo, and aryloxo ligands is described including Brønsted acid/base reactions, coordination, and activation of polar substrates toward N–C bond forming reactions and metal‐mediated activation of dihydrogen and C–H bonds. The impact of ancillary ligands and Ru oxidation states (RuII versus RuIII) are discussed. In addition, the preparation and reactivity of well‐defined monomeric two‐ and three‐coordinate Cu complexes with amido, alkoxo, hydroxo, and aryloxo ligands are presented including examples of reactions to probe fundamental reactivity patterns as well as catalytic addition of N–H and O–H bonds across C=C bonds of olefins. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)