Dinitrogen complexes File:RuA5N2.png|thumb|right|Structure of [Ru(NH3)5(N2)]2+ (
pentaamine(dinitrogen)ruthenium(II)), the first dinitrogen complex to be discovered The first example of a
dinitrogen complex to be discovered was [Ru(NH3)5(N2)]2+ (see figure at right), and soon many other such complexes were discovered. These
complexes, in which a nitrogen molecule donates at least one lone pair of electrons to a central metal cation, illustrate how N2 might bind to the metal(s) in
nitrogenase and the
catalyst for the
Haber process: these processes involving dinitrogen activation are vitally important in biology and in the production of fertilisers. Dinitrogen is able to coordinate to metals in five different ways. The more well-characterised ways are the end-on M←N≡N (
η1) and M←N≡N→M (
μ, bis-
η1), in which the lone pairs on the nitrogen atoms are donated to the metal cation. The less well-characterised ways involve dinitrogen donating electron pairs from the triple bond, either as a
bridging ligand to two metal cations (
μ, bis-
η2) or to just one (
η2). The fifth and unique method involves triple-coordination as a bridging ligand, donating all three electron pairs from the triple bond (
μ3-N2). A few complexes feature multiple N2 ligands and some feature N2 bonded in multiple ways. Since N2 is isoelectronic with
carbon monoxide (CO) and
acetylene (C2H2), the bonding in dinitrogen complexes is closely allied to that in
carbonyl compounds, although N2 is a weaker
σ-donor and
π-acceptor than CO. Theoretical studies show that
σ donation is a more important factor allowing the formation of the M–N bond than
π back-donation, which mostly only weakens the N–N bond, and end-on (
η1) donation is more readily accomplished than side-on (
η2) donation. :3 Ca + N2 → Ca3N2 :3 Mg + 2 NH3 → Mg3N2 + 3 H2 (at 900 °C) :3 Zn(NH2)2 → Zn3N2 + 4 NH3 Many variants on these processes are possible. The most ionic of these nitrides are those of the
alkali metals and
alkaline earth metals, Li3N (Na, K, Rb, and Cs do not form stable nitrides for steric reasons) and M3N2 (M = Be, Mg, Ca Sr, Ba). These can formally be thought of as salts of the N3− anion, although charge separation is not actually complete even for these highly electropositive elements. However, the alkali metal
azides NaN3 and KN3, featuring the linear anion, are well-known, as are Sr(N3)2 and Ba(N3)2. Azides of the B-subgroup metals (those in
groups 11 through
16) are much less ionic, have more complicated structures, and detonate readily when shocked. Industrially,
ammonia (NH3) is the most important compound of nitrogen and is prepared in larger amounts than any other compound because it contributes significantly to the nutritional needs of terrestrial organisms by serving as a precursor to food and fertilisers. It is a colourless alkaline gas with a characteristic pungent smell. The presence of
hydrogen bonding has very significant effects on ammonia, conferring on it its high melting (−78 °C) and boiling (−33 °C) points. As a liquid, it is a very good solvent with a high heat of vaporisation (enabling it to be used in vacuum flasks), that also has a low viscosity and electrical conductivity and high
dielectric constant, and is less dense than water. However, the hydrogen bonding in NH3 is weaker than that in H2O due to the lower electronegativity of nitrogen compared to oxygen and the presence of only one lone pair in NH3 rather than two in H2O. It is a weak base in aqueous solution (
pKb 4.74); its conjugate acid is
ammonium, . It can also act as an extremely weak acid, losing a proton to produce the amide anion, . It thus undergoes self-dissociation, similar to water, to produce ammonium and amide. Ammonia burns in air or oxygen, though not readily, to produce nitrogen gas; it burns in fluorine with a greenish-yellow flame to give
nitrogen trifluoride. Reactions with the other nonmetals are very complex and tend to lead to a mixture of products. Ammonia reacts on heating with metals to give nitrides. Many other binary nitrogen hydrides are known, but the most important are
hydrazine (N2H4) and
hydrogen azide (HN3). Although it is not a nitrogen hydride,
hydroxylamine (NH2OH) is similar in properties and structure to ammonia and hydrazine as well. Hydrazine is a fuming, colourless liquid that smells similar to ammonia. Its physical properties are very similar to those of water (melting point 2.0 °C, boiling point 113.5 °C, density 1.00 g/cm3). Despite it being an endothermic compound, it is kinetically stable. It burns quickly and completely in air very exothermically to give nitrogen and water vapour. It is a very useful and versatile reducing agent and is a weaker base than ammonia. Hydrazine is generally made by reaction of ammonia with alkaline
sodium hypochlorite in the presence of gelatin or glue: :NH3 + OCl− → NH2Cl + OH− :NH2Cl + NH3 → + Cl− (slow) : + OH− → N2H4 + H2O (fast) (The attacks by hydroxide and ammonia may be reversed, thus passing through the intermediate NHCl− instead.) The reason for adding gelatin is that it removes metal ions such as Cu2+ that catalyses the destruction of hydrazine by reaction with
monochloramine (NH2Cl) to produce
ammonium chloride and nitrogen.
Nitrogen trifluoride (NF3, first prepared in 1928) is a colourless and odourless gas that is thermodynamically stable, and most readily produced by the
electrolysis of molten
ammonium fluoride dissolved in anhydrous
hydrogen fluoride. Like
carbon tetrafluoride, it is not at all reactive and is stable in water or dilute aqueous acids or alkalis. Only when heated does it act as a fluorinating agent, and it reacts with
copper, arsenic, antimony, and bismuth on contact at high temperatures to give
tetrafluorohydrazine (N2F4). The cations and are also known (the latter from reacting tetrafluorohydrazine with strong fluoride-acceptors such as
arsenic pentafluoride), as is ONF3, which has aroused interest due to the short N–O distance implying partial double bonding and the highly polar and long N–F bond. Tetrafluorohydrazine, unlike hydrazine itself, can dissociate at room temperature and above to give the radical NF2•.
Fluorine azide (FN3) is very explosive and thermally unstable.
Dinitrogen difluoride (N2F2) exists as thermally interconvertible
cis and
trans isomers, and was first found as a product of the thermal decomposition of FN3. For this reason, small amounts of nitrogen triiodide are sometimes synthesised as a demonstration to high school chemistry students or as an act of "chemical magic".
Chlorine azide (ClN3) and
bromine azide (BrN3) are extremely sensitive and explosive. Two series of nitrogen oxohalides are known: the nitrosyl halides (XNO) and the nitryl halides (XNO2). The first is very reactive gases that can be made by directly halogenating nitrous oxide.
Nitrosyl fluoride (NOF) is colourless and a vigorous fluorinating agent.
Nitrosyl chloride (NOCl) behaves in much the same way and has often been used as an ionising solvent.
Nitrosyl bromide (NOBr) is red. The reactions of the nitryl halides are mostly similar:
nitryl fluoride (FNO2) and
nitryl chloride (ClNO2) are likewise reactive gases and vigorous halogenating agents. and N(NO2)3 (
trinitramide). All are thermally unstable towards decomposition to their elements. One other possible oxide that has not yet been synthesised is
oxatetrazole (N4O), an aromatic ring. It is formed by catalytic oxidation of ammonia. It is a colourless paramagnetic gas that, being thermodynamically unstable, decomposes to nitrogen and oxygen gas at 1100–1200 °C. Its bonding is similar to that in nitrogen, but one extra electron is added to a
π* antibonding orbital and thus the bond order has been reduced to approximately 2.5; hence dimerisation to O=N–N=O is unfavourable except below the boiling point (where the
cis isomer is more stable) because it does not actually increase the total bond order and because the unpaired electron is delocalised across the NO molecule, granting it stability. There is also evidence for the asymmetric red dimer O=N–O=N when nitric oxide is condensed with polar molecules. It reacts with oxygen to give brown nitrogen dioxide and with halogens to give nitrosyl halides. It also reacts with transition metal compounds to give nitrosyl complexes, most of which are deeply coloured. It is a
deliquescent, colourless crystalline solid that is sensitive to light. In the solid state it is ionic with structure [NO2]+[NO3]−; as a gas and in solution it is molecular O2N–O–NO2. Hydration to nitric acid comes readily, as does analogous reaction with
hydrogen peroxide giving
peroxonitric acid (HOONO2). It is a violent oxidising agent. Gaseous dinitrogen pentoxide decomposes as follows:
Nitrous acid (HNO2) is not known as a pure compound, but is a common component in gaseous equilibria and is an important aqueous reagent: its aqueous solutions may be made from acidifying cool aqueous
nitrite (, bent) solutions, although already at room temperature disproportionation to
nitrate and nitric oxide is significant. It is a weak acid with p
Ka 3.35 at 18 °C. They may be
titrimetrically analysed by their oxidation to nitrate by
permanganate. They are readily reduced to nitrous oxide and nitric oxide by
sulfur dioxide, to hyponitrous acid with
tin(II), and to ammonia with
hydrogen sulfide. Salts of
hydrazinium react with nitrous acid to produce azides which further react to give nitrous oxide and nitrogen.
Sodium nitrite is mildly toxic in concentrations above 100 mg/kg, but small amounts are often used to cure meat and as a preservative to avoid bacterial spoilage. It is also used to synthesise hydroxylamine and to
diazotise primary aromatic amines as follows: The amount of nitrogen in a
chemical substance can be determined by the
Kjeldahl method. In particular, nitrogen is an essential component of
nucleic acids,
amino acids and thus
proteins, and the energy-carrying molecule
adenosine triphosphate and is thus vital to all life on Earth. ==Occurrence==