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

The preparation and reactivity of late transition-metal complexes in low oxidation states with nondative-hetero atomic ligands (e.g., amido, hydroxo, alkoxo, and aryloxo ligands) are described. For such complexes the disruption of ligand-to-metal pi-donation because of a filled d pi manifold can enhance the nucleophilic and/or basic reactivity at the non-dative-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 Bronsted 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 (Ru-II versus Ru-III) 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. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)