Nitrogen has electronic configuration [He]2s22p3,
and accessible oxidation states from -3 to +5. It has more valence
electrons than orbitals (2x2s and 3x2p = 5, in 4 orbitals),
so lone pairs play an important
role in its chemistry.
N2 is inert; the very strong N-N triple
bond is very stable towards decomposition and reaction, and
this means that nitrogen gas is often used to make an inert
atmosphere for the handling of and manufacture of oxygen sensitive
compounds.
The N-N single bond is, however, weak; all N-X
bonds are weak, with the exception of N-H, due to the presence
of the strong electrostatic repulsion between non-bonded
electrons on the adjacent atoms (an example of the influence
of the lone pair on N). N therefore has a tendency to form strong,
multiple bonds, such as N=O, N=S, N=C, and the triple bonds
in N2 and -CN (the cyanide
group), and many N containing compounds are unstable with respect
to the formation of N2. (For a comparison between
the chemistries of nitrogen and phosphorous, click here.)
N2 bonds to metals in a synergic
bonding process in much the same way as Carbon Monoxide
(CO), with which it is isoelectronic.
Here, there is donation of the N lone pair electrons to form
a M-N σ-bond, and then back donation
of electrons from the metal into the antibonding π*-orbitals
on the N.

The above reaction may give some indication
of the kind of process happening in the fixation
of N2 in soils (the catalytic conversion to NH4+
by the enzyme nitrogenase). A similar reaction in the tungsten
compound yields NH4+ from the N2
containing reactant.

Occurrence
Nitrogen occurs mainly as N2 (g) (~79% of the atmosphere) and is obtained
by the distillation of liquid air.
Nitrides
These are often difficult to classify. The N3- ion is highly charged and
so is is only stabilized by small, highly polarizing cations,
such as Li+ and Mg2+, and formulation
of N as N3- might not be correct. In Li3N,
it is better to think of the compound as (Li2N)-Li+,
as demonstrated by the layer structure.
Structure of Li3N |
| Layered structure consisting of hexagons
of Li+ ions with N3- at the centers
(Li2N)-, with Li+ ions
bridging the layers, sited between two N ions. |
 |
|