Three energetic coordination compounds with strong reducibility were prepared with cyanoborohydride （CBH） as anion， 1-vinyl imidazole （VIM） as ligand and transition metals Co， Mn and Ni as central ions. The crystal structures were determined by single crystal X-ray diffraction and their molecular formulas are Co（VIM）₄（CBH）₂， Mn（VIM）₄（CBH）₂ and Ni（VIM）₄（CBH）₂， respectively. The thermal decomposition performance， oxygen bomb calorimetry and mechanical sensitivities of the complexes were tested. The results show that the complexes have high burning calorific capacity （26.5-29.1 kJ·g^-1）， low friction sensitivity （>360 N） and impact sensitivity （>40 J）. Hypergolic testing with white fuming nitric acid shows that the complexes can combust spontaneously， and the ignition delay time is short （4-13 ms）， which confirm the high reduction activity of the complexes. To explore the application of active coordination compounds in initiating explosive devices， three new composite igniting powders were obtained by mixing three complexes with sodium bromate in the mass ratio of 1∶7， respectively. The composite powders were ignited and tested with electric heating wire. After being ignited by electric heating wire， the three composite agents can burn continuously and produce large flame. Results show that the composite agents have potential applications as new ignition agents.