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Concept
Transition metal hydride
Résumé
Transition metal hydrides are chemical compounds containing a transition metal bonded to hydrogen. Most transition metals form hydride complexes and some are significant in various catalytic and synthetic reactions. The term "hydride" is used loosely: some of them are acidic (e.g., H2Fe(CO)4), whereas some others are hydridic, having H−-like character (e.g., ZnH2).
Binary compounds of hydrogen
Many transition metals form compounds with hydrogen. These materials are called binary hydrides, because they contain only two elements. The hydrogenic ligand is assumed to have hydridic (H−-like) character. These compounds are invariably insoluble in all solvents, reflecting their polymeric structures. They often exhibit metal-like electrical conductivity. Many are nonstoichiometric compounds. Electropositive metals (Ti, Zr, Hf, Zn) and some other metals form hydrides with the stoichiometry MH or sometimes MH2 (M = Ti, Zr, Hf, V, Zn). The best studied are the binary hydrides of palladium, which readily forms a limiting monohydride. In fact, hydrogen gas diffuses through Pd windows via the intermediacy of PdH.
Ternary metal hydrides have the formula AxMHn, where A+ is an alkali or alkaline earth metal cation, e.g. K+ and Mg2+. A celebrated example is K2ReH9, a salt containing two K+ ions and the ReH92− anion. Other homoleptic metal hydrides include the anions in Mg2FeH6 and Mg2NiH4. Some of these anionic polyhydrides satisfy the 18-electron rule, many do not. Because of their high lattice energy, these salts are typically not soluble in any solvents, a well known exception being K2ReH9.
The most prevalent hydrides of the transition metals are metal complexes that contain a mix of ligands in addition to hydride. The range of coligands is large. Virtually all of the metals form such derivatives. The main exceptions include the late metals silver, gold, cadmium, and mercury, which form few or unstable complexes with direct M-H bonds. Examples of an industrially useful hydrides are HCo(CO)4 and HRh(CO)(PPh3)3, which are catalysts for hydroformylation.
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