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iron 2 nitride is an industrially important compound obtained by heating reduced ferrous chloride or nitrate in the presence of nitrogen under pressure. However, merely exposing iron to nitrogen at its ordinary temperature does not yield any perceptible quantity of nitride, even under high pressures. The reason for this is the development of void channels and pore structures within the layer, which slow down the diffusion of nitrogen to the centre of the compound, and hence also the growth rate of the austenite structure.
An attempt has been made to speed up nitrogen evolution in this system by a sequence of proton and electron transfers within the b-diketiminate iron system, where isolable nitride, imide and amide intermediates have been observed. The zero-field Mossbauer spectrum of solid 3 at 173 K reveals two quadrupole doublets in a 2 : 1 ratio, suggesting that the sterically congested m3-bridging nitride ligand is protonated first, followed by rapid PCET to the diiron imide/amide product 5.
This reaction can be carried out under very high pressures (up to 18 atmospheres). The experimental results show that nitrogen evolution takes place to first order in the concentration of the interstitial nitrogen and to second order in its concentration on the surface of the particles, with E = 165 kJ mole-1. The experimental kinetics are in good agreement with theoretical calculations. Furthermore, it is shown that the reactivity of the nitride ligands in the starting complex 1 can be enhanced by introducing a third bridging nitride atom, resulting in a triiron nitride/imide complex with an overall increase in reactivity.