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New developments in the synthesis, crystal and molecular structure, spectroscopy and kinetic properties of the [M(CN) 5 L] n − ions (M II,III =Fe, Ru, Os; L=H 2 O, NH 3 , amines, CN − , N -heterocyclic ligands, etc.), performed over the last decade, are reviewed. The properties of dinuclear complexes containing pentacyano-fragments bridged by pyrazine, cyanide or other bridging ligands, are also considered, with emphasis on mixed-valent systems. The influence of the solvent and other medium effects on the electronic structure, as well as on the modification of the reactivity of L upon coordination is addressed particularly. Some catalytic processes relevant to bioinorganic chemistry are discussed, involving either ligand oxidation (hydrazine, thiolates) or reduction (nitrosyl). |
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