期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 -, 期 9, 页码 1185-1203出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.200601072
关键词
nondative heteroatomic ligands; ruthenium; copper; C-H activation
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)
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