Nitrides

Key point: Nitrides are classified as saline, covalent, or interstitial. The nitrides of metals can be prepared by direct interaction of the element with nitrogen or ammonia or by thermal decomposition of an amide:

The compounds of N with H, O, and the halogens are treated separately. The saline nitrides can be regarded as containing the nitride ion, N₃. However, the high charge of this ion means that it is highly polarizing (Section 1.9e) and saline nitrides are likely to have considerable covalent character. Saline nitrides occur for lithium, Li₃N, and the Group 2 elements, M₃N₂. The covalent nitrides, in which the E-N bond is covalent, possess a wide range of properties depending on the element to which N is bonded. Some examples of covalent nitrides are boron nitride, BN, cyanogen, (CN)₂, phosphorus nitride, P₃N₅, tetra sulfur tetranitride, S₄N₄, and disulfur dinitride, S₂N₂. These compounds are discussed in the context of the other elements. The largest category of nitrides consists of the interstitial nitrides of the d-block elements with formula MN, M₂N, or M₄N. The N atom occupies some or all of the octahedral sites within the cubic or hexagonal close-packed lattice of metal atoms. The compounds are hard and inert, with a metallic lustre and conductivity. They are widely used as refractory materials and find applications as crucibles, high-temperature reaction vessels, and thermocouple sheaths. The nitrideion, N₃, is often found as a ligand in d-metal complexes. Its high negative charge, small size, and ability to serve as a good π-donor as well as a σ-donor, means that it can stabilize metals in high oxidation states. The short coordinate bond between the ion and the metal atom is often represented as MN. An example is the complex [Os(N)(NH₃)₅]²⁺(10).

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مواضيع ذات صلة

Phosphine, arsane, and stibine

Hydrazine and hydroxylamine

Ammonia

Phosphides

Azides

Nitrogen activation

Microporous solids

Aluminosilicates

Compounds with nitrogen

Oxides of germanium, tin, and lead

Compounds of carbon with oxygen and sulfur

Tin and lead halides