Roads to pentazolate anion: a theoretical insight.

The formation mechanism of pentazolate anion (PZA) is not yet clear. In order to present the possible formation pathways of PZA, the potential energy surfaces of phenylpentazole (PPZ), phenylpentazole radical (PPZ-R), phenylpentazole radical anion (PPZ-RA), PPZ and -chloroperbenzoic acid (-CPBA), -pentazolylphenolate anion (-PZPolA) and -CPBA, and -pentazolylphenol (-PZPol) and -CPBA were calculated by the computational electronic structure methods including the hybrid density functional, the double hybrid density functional and the coupled-cluster theories. At the thermodynamic point of view, the cleavages of C-N bonds of PPZ and PPZ-R need to absorb large amounts of heat. Thus, they are not feasible entrance for PZA formation at ambient condition. But excitation of PPZ and deprotonation of PPZ-RA probably happen before cleavage of C-N bond of PPZ at high-energy condition. As to the radical anion mechanism, the high accuracy calculations surveyed that the barrier of PZA formation is probably lower than that of dinitrogen evolution, but the small ionization potential of PPZ-RA gives rise to the unstable ionic pair of sodium PPZ at high temperature. In respect of oxidation mechanism, except for PPZ, the reactions of -PZPolA and -PZPol with -CPBA can form PZA and quinone. The PZA formations have the barriers of about 20 kcal mol which compete with the dinitrogen evolutions. The stabilities of PZA in both solid and gas phases were also studied herein. The proton prefers to transfer to pentazolyl group in the (N)(HO)(NH)Cl system which leads to the dissociation of pentazole ring. The ground states of M(N)(HO) (M = Co, Fe and Mn) are high-spin states. The pentazolyl groups confined by the crystal waters in the coordinate compounds can improve the kinetic stability. As to the reactivity of PZA, it can be persistently oxidized by -CPBA to oxo-PZA and 1,3-oxo-PZA with the barriers of about 20 kcal mol.