Гидриды: свойства, применение и роль в химии

binary compounds of hydrogen with another elementMolecule with a hydrogen bound to a more electropositive element or group
In chemistry, a hydride is formally the anion of hydrogen (H−), a hydrogen atom with two electrons. The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are also called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed. Almost all of the elements form binary compounds with hydrogen, the exceptions being He, Ne, Ar, Kr, Pm, Os, Ir, Rn, Fr, and Ra.]] Hydrides such as sodium borohydride, lithium aluminium hydride, diisobutylaluminium hydride (DIBAL) and super hydride, are commonly used as reducing agents in chemical synthesis. The hydride adds to an electrophilic center, typically unsaturated carbon. Hydrides such as sodium hydride and potassium hydride are used as strong bases in organic synthesis. The hydride reacts with the weak Bronsted acid releasing H2. Hydrides such as calcium hydride are used as desiccants, i. e. drying agents, to remove trace water from organic solvents. The hydride reacts with water forming hydrogen and hydroxide salt. The dry solvent can then be distilled or vacuum transferred from the "solvent pot". Hydrides are important in storage battery technologies such as nickel metal hydride battery. Various metal hydrides have been examined for use as a means of hydrogen storage for fuel cell powered electric cars and other purposed aspects of a hydrogen economy. Hydride complexes are catalysts and catalytic intermediates in a variety of homogeneous and heterogeneous catalytic cycles. Important examples include hydrogenation, hydroformylation, hydrosilylation, hydrodesulfurization catalysts. Even certain enzymes, the hydrogenase, operate via hydride intermediates. The energy carrier nicotinamide adenine dinucleotide reacts as a hydride donor or hydride equivalent.

According to some definitions, covalent hydrides cover all other compounds containing hydrogen. Some definitions limit hydrides to hydrogen centres that formally react as hydrides, i. e. are nucleophilic, and hydrogen atoms bound to metal centers. These hydrides are formed by all the true non metals (except zero group elements) and the elements like Al, Ga, Sn, Pb, Bi, Po, etc., which are normally metallic in nature, i. e., this class includes the hydrides of p block elements. In these substances the hydride bond is formally a covalent bond much like the bond made by a proton in a weak acid. This category includes hydrides that exist as discrete molecules, polymers or oligomers, and hydrogen that has been chem adsorbed to a surface. A particularly important segment of covalent hydrides are complex metal hydrides, powerful soluble hydrides commonly used in synthetic procedures. Molecular hydrides often involve additional ligands; for example, diisobutylaluminium hydride (DIBAL) consists of two aluminum centers bridged by hydride ligands. Hydrides that are soluble in common solvents are widely used in organic synthesis. Particularly common are sodium borohydride (|NaBH4) and lithium aluminium hydride and hindered reagents such as DIBAL.

Interstitial hydrides most commonly exist within metals or alloys. They are traditionally termed "compounds" even though they do not strictly conform to the definition of a compound, more closely resembling common alloys such as steel. In such hydrides, hydrogen can exist as either atomic or diatomic entities. Mechanical or thermal processing, such as bending, striking, or annealing, may cause the hydrogen to precipitate out of solution by degassing. Their bonding is generally considered metallic. Such bulk transition metals form interstitial binary hydrides when exposed to hydrogen. These systems are usually non stoichiometric, with variable amounts of hydrogen atoms in the lattice. In materials engineering, the phenomenon of hydrogen embrittlement results from the formation of interstitial hydrides. Hydrides of this type form according to either one of two main mechanisms. The first mechanism involves the adsorption of dihydrogen, succeeded by the cleaving of the H H bond, the delocalisation of the hydrogen's electrons, and finally the diffusion of the protons into the metal lattice. The other main mechanism involves the electrolytic reduction of ionised hydrogen on the surface of the metal lattice, also followed by the diffusion of the protons into the lattice. The second mechanism is responsible for the observed temporary volume expansion of certain electrodes used in electrolytic experiments. Palladium absorbs up to 900 times its own volume of hydrogen at room temperatures, forming palladium hydride. This material has been discussed as a means to carry hydrogen for vehicular fuel cells. Interstitial hydrides show certain promise as a way for safe hydrogen storage. Neutron diffraction studies have shown that hydrogen atoms randomly occupy the octahedral interstices in the metal lattice (in an fcc lattice there is one octahedral hole per metal atom). The limit of absorption at normal pressures is PdH0.7, indicating that approximately 70% of the octahedral holes are occupied. Many interstitial hydrides have been developed that readily absorb and discharge hydrogen at room temperature and atmospheric pressure. They are usually based on intermetallic compounds and solid solution alloys. However, their application is still limited, as they are capable of storing only about 2 weight percent of hydrogen, insufficient for automotive applications.

Transition metal hydrides include compounds that can be classified as covalent hydrides. Some are even classified as interstitial hydrides and other bridging hydrides. Classical transition metal hydride feature a single bond between the hydrogen centre and the transition metal. Some transition metal hydrides are acidic, e. g., |HCo(CO)4 and |H2Fe(CO)4. The anions potassium nonahydridorhenate |[ReH9](2 ) and |[FeH6](4 ) are examples from the growing collection of known molecular homoleptic metal hydrides. As pseudohalides, hydride ligands are capable of bonding with positively polarized hydrogen centres. This interaction, called dihydrogen bonding, is similar to hydrogen bonding, which exists between positively polarized protons and electronegative atoms with open lone pairs.

Hydrides containing protium are known as protides.

Hydrides containing deuterium are known as deuterides. Some deuterides, such as LiD, are important fusion fuels in thermonuclear weapons and useful moderators in nuclear reactors.

Hydrides containing tritium are known as tritides.

Mixed anion compounds exist that contain hydride with other anions. These include boride hydrides, carbohydrides, hydridonitrides, oxyhydrides and others.

According to IUPAC convention, by precedence (stylized electronegativity), hydrogen falls between group 15 and group 16 elements. Therefore, we have NH3, "nitrogen hydride" (ammonia), versus H2O, "hydrogen oxide" (water). This convention is sometimes broken for polonium, which on the grounds of polonium's metallicity is often referred to as "polonium hydride" instead of the expected "hydrogen polonide".