Abstract
This review presents a new structural feature related to the hydrolysis of metal ions, which has been revealed during the past four years. It concerns a new form of bridging between metal ions. An OH ligand coordinated to a metal atom may form a short and symmetrical hydrogen bond to an H2O ligand of another metal atom, thereby forming a hydrogen oxide bridging ligand (H3O −2 ) between these atoms. This ligand was first discovered and recognized as such in 1981 by X-ray diffraction studies of some crystalline salts of trinuclear triangular cluster ions of molybdenum and tungsten. It has since been shown to exist also in classical coordination compounds. This ligand plays a fundamental role in the structure of primary hydrolysis products of metal ions. Some of these products, formerly believed to be mononuclear, such as the socalled hydroxoaqua ions [ML4(H2O)(OH)](n−1)+ were shown to be dimers or chain-polymers in which the metal atoms are bridged by hydrogen oxide ligands. While X-ray studies established the existence of hydrogen oxide bridged dimers in crystalline hydrolysis products of metal ions, other physico-chemical methods were used to demonstrate the persistence of these structures in aqueous solutions. The impact of these findings on the overall picture of hydrolysis and in particular on reaction mechanisms of redox and substitution reactions is discussed.
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Ardon, M., Bino, A. (1987). A new aspect of hydrolysis of metal ions: The hydrogen-oxide bridging ligand (H3O −2 ). In: Solid State Chemistry. Structure and Bonding, vol 65. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0004457
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