Theoretical study on the tautomerization of 1,5-diaminotetrazole (DAT)

摘要

The tautomerization pathways and kinetics of 1,5-diaminotetrazole (DAT) have been investigated by means of second-order M?ller-Plesset perturbation theory (MP2) and coupled-cluster theory, with single and double excitations including perturbative corrections for triple excitations (CCSD(T)). Five possible tautomers, namely 4-hydro-1-amino-5-imino-tetrazole (a), 2,5-diamino-tetrazole (b), 1,5-diamino-tetrazole (c), 2-hydro-1-imino-5-amino-tetrazole (d), and 2,4-dihydro-1,5-diimino-tetrazole (e) were identified. The structures of the reactants, transition states, and products along with the tautomerism pathways were optimized by the MP2 method using the 6-311G~(**) basis set, and the energies were refined using CCSD(T)/6-311G~(**). The minimum-energy path (MEP) information for DAT was obtained at the CCSD(T)/6-311G~(**)//MP2/6-311G~(**) level of theory. Therein, reaction 2 (c → b) is an amino-shift reaction, while reaction 1 (c → a), reaction 3 (c → d), reaction 4 (a → e), and reaction 5 (d → e) are reactions of hydrogen-shift tautomerization. The calculated results show that 2,5-diaminotetrazole (b) with the minimum energy (taking c as a standard) among five tautomers, is the energetically preferred tautomer of DAT in the gas phase. In addition, the energy barrier of reaction 2 is 71.65 kcal ·mol~(?1) in the gas phase, while reaction 1 takes place more easily with an activation barrier of 61.53 kcal·mol~(?1) also as compared to 63.71 kcal·mol~(?1) in reaction 3. Moreover, the tautomerization of reaction 4 requires the largest energy barrier of 83.29 kcal·mol~(?1), which is obviously bigger than reaction 5 with a value of 73.78 kcal ·mol~(?1). Thus, the hydrogen-shift of c to a is the easiest transformation, while the tautomerization of a to e is the hardest one. Again, the rate constants of tautomerization have been obtained by TST, TST/Eckart, CVT, CVT/SCT, and CVT/ZCT methods in the range 200-2500 K, and analysis indicated that variational effects are small over the whole temperature range, while tunneling effects are significant in the lower temperature range.