The binary nitrogen halides are thermodynamically unstable with respect to decomposition to the elements, with the exception of NF₃.

NF₃ has a much lower dipole moment than ammonia, and has no σ-donor properties. This is because F is more electronegative than N, and hence the N lone pair is polarized towards the F atoms (NF₃ is N^δ+(F^δ-)₃, whereas NH₃ is N^δ-(H^δ+)₃), and is therefore unavailable to act as an electron pair donor. It is inert to reaction with acids and alkalis, but does react with fluoride ion Lewis acid acceptors to produce a N^V species:

NCl₃: This is a volatile and explosive, and is hydrolyzed to give ammonia and hypochlorite ions.

NBr₃ and NI₃: these are very unstable and are not known free of ammonia.

N2F4: this exists in equilibrium between the gauche- and trans-structures