摘要
The effect of metallic ions on the nitrolysis of DAPT [3,7-diacetyl-1,3,5,7-tetraazabicyclo（3.3.1）nonane] and HA （hexamine） was investigated by experimental and theoretical approaches. The combinatorial reagent, M（NO3）n/Ac20/NH4NO3 （M=Mg2＋, Cu2＋, Pb2＋, Bi3＋, Fe3＋ and Zr4＋）, was found to be efficient in the experiment of the nitrolysis of DAPT. A key intermediate during the nitrolysis of DAPT was detected by 1H NMR. The formation mechanism of the intermediate was proposed and analyzed. Some discrepant results for the nitrolysis of DAPT and HA catalyzed by different metallic nitrates were explained based on hard-soft and acid-base principle and stabilized energy of ion-complex. From the latter point of view, some cations with high polarizable ligands, e.g., O802CF3-, （CF3SO2）2N-, and （C4F9SO2）2N-, can increase the yields. Two newly designed catalysts, Cu[（CF3SO2）2N]2 and Cu[（C4F9SO2）2N]2, were tested to be highly efficient.
The effect of metallic ions on the nitrolysis of DAPT [3,7-diacetyl-1,3,5,7-tetraazabicyclo（3.3.1）nonane] and HA （hexamine） was investigated by experimental and theoretical approaches. The combinatorial reagent, M（NO3）n/Ac20/NH4NO3 （M=Mg2＋, Cu2＋, Pb2＋, Bi3＋, Fe3＋ and Zr4＋）, was found to be efficient in the experiment of the nitrolysis of DAPT. A key intermediate during the nitrolysis of DAPT was detected by 1H NMR. The formation mechanism of the intermediate was proposed and analyzed. Some discrepant results for the nitrolysis of DAPT and HA catalyzed by different metallic nitrates were explained based on hard-soft and acid-base principle and stabilized energy of ion-complex. From the latter point of view, some cations with high polarizable ligands, e.g., O802CF3-, （CF3SO2）2N-, and （C4F9SO2）2N-, can increase the yields. Two newly designed catalysts, Cu[（CF3SO2）2N]2 and Cu[（C4F9SO2）2N]2, were tested to be highly efficient.
