A series of potentially explosive Werner-type cobalt(Ⅲ)complexes comprising the anions azotetrazolate,nitrotetrazolate,picrate and dipicrylamide were prepared via simple metathetical routes.Treatment of[Co(NH_(3))_(5...A series of potentially explosive Werner-type cobalt(Ⅲ)complexes comprising the anions azotetrazolate,nitrotetrazolate,picrate and dipicrylamide were prepared via simple metathetical routes.Treatment of[Co(NH_(3))_(5)NO_(2)]Cl_(2),trans-[Co(NH_(3))_(4)(py)NO_(2)]Cl_(2)(py=pyridine),trans-[Co(NH_(3))_(4)(NO_(2))_(2)]Cl,and[Co(NH_(3))_(5)N_(3)]Cl_(2)with equimolar amounts of disodium azotetrazolate,(Na_(2)C_(2)N_(10)·5H_(2)O,1),in aqueous solutions afforded new cobalt(Ⅲ)azotetrazolate salts[Co(NH_(3))_(5)NO_(2)](C_(2)N_(10))·2H_(2)O(2),trans-[Co(NH_(3))_(4)(py)-NO_(2)](C_(2)N_(10))·2H_(2)O_(3),trans-[Co(NH_(3))_(4)(NO_(2))_(2)]2(C_(2)N_(10))(4),and[Co(NH_(3))_(5)N_(3)](C_(2)N_(10))·H_(2)O(5)in moderate to excellent yields(46–88%).Similar treatment of trans-[Co(NH_(3))_(4)(NO_(2))_(2)]Cl with 1 equiv.of sodium 5-nitrotetrazolate dihydrate(=NaNT,6)afforded the novel cobalt(Ⅲ)5-nitrotetrazolate derivative trans-[Co(NH_(3))_(4)(NO_(2))_(2)](NT)·H_(2)O(7)as orange,rectangular prismatic crystals in 64%yield.Two complex cobalt(Ⅲ)picrates,trans-[Co(NH_(3))_(4)(NO_(2))_(2)](picrate)·H_(2)O(9)and[Co(NH_(3))_(5)N_(3)](picrate)2(10),were prepared in a similar manner from the corresponding chloride precursors and equimolar amounts of sodium picrate.The reaction of trans-[Co(NH_(3))_(4)(NO_(2))_(2)]Cl with sodium dipicrylamide(=NaDPA)in a 1:1 molar ratio gave the first cobalt(Ⅲ)dipicrylamide,trans-[Co(NH_(3))_(4)(NO_(2))_(2)](DPA)·H_(2)O(12).Finally,the highly explosive,dark blue-green dichroitic non-electrolyte complex mer-[Co(en)(py)(N_(3))_(3)](13)was formed upon treatment of[Co(en)(py)_(2)(NH_(3))Cl]Cl_(2)·H_(2)O with excess NaN_(3)in hot water(93%yield).The molecular and crystal structures of 2,3,4,5,7,9,10,12,and 13 were determined by single-crystal X-ray diffraction.In the solid state,all compounds comprised extensive hydrogen-bonded supramolecular networks.Representative studies of the energetic properties(impact and friction sensitivity,combustion)revealed that some of the new compounds can be classified as primary explosives.展开更多
文摘A series of potentially explosive Werner-type cobalt(Ⅲ)complexes comprising the anions azotetrazolate,nitrotetrazolate,picrate and dipicrylamide were prepared via simple metathetical routes.Treatment of[Co(NH_(3))_(5)NO_(2)]Cl_(2),trans-[Co(NH_(3))_(4)(py)NO_(2)]Cl_(2)(py=pyridine),trans-[Co(NH_(3))_(4)(NO_(2))_(2)]Cl,and[Co(NH_(3))_(5)N_(3)]Cl_(2)with equimolar amounts of disodium azotetrazolate,(Na_(2)C_(2)N_(10)·5H_(2)O,1),in aqueous solutions afforded new cobalt(Ⅲ)azotetrazolate salts[Co(NH_(3))_(5)NO_(2)](C_(2)N_(10))·2H_(2)O(2),trans-[Co(NH_(3))_(4)(py)-NO_(2)](C_(2)N_(10))·2H_(2)O_(3),trans-[Co(NH_(3))_(4)(NO_(2))_(2)]2(C_(2)N_(10))(4),and[Co(NH_(3))_(5)N_(3)](C_(2)N_(10))·H_(2)O(5)in moderate to excellent yields(46–88%).Similar treatment of trans-[Co(NH_(3))_(4)(NO_(2))_(2)]Cl with 1 equiv.of sodium 5-nitrotetrazolate dihydrate(=NaNT,6)afforded the novel cobalt(Ⅲ)5-nitrotetrazolate derivative trans-[Co(NH_(3))_(4)(NO_(2))_(2)](NT)·H_(2)O(7)as orange,rectangular prismatic crystals in 64%yield.Two complex cobalt(Ⅲ)picrates,trans-[Co(NH_(3))_(4)(NO_(2))_(2)](picrate)·H_(2)O(9)and[Co(NH_(3))_(5)N_(3)](picrate)2(10),were prepared in a similar manner from the corresponding chloride precursors and equimolar amounts of sodium picrate.The reaction of trans-[Co(NH_(3))_(4)(NO_(2))_(2)]Cl with sodium dipicrylamide(=NaDPA)in a 1:1 molar ratio gave the first cobalt(Ⅲ)dipicrylamide,trans-[Co(NH_(3))_(4)(NO_(2))_(2)](DPA)·H_(2)O(12).Finally,the highly explosive,dark blue-green dichroitic non-electrolyte complex mer-[Co(en)(py)(N_(3))_(3)](13)was formed upon treatment of[Co(en)(py)_(2)(NH_(3))Cl]Cl_(2)·H_(2)O with excess NaN_(3)in hot water(93%yield).The molecular and crystal structures of 2,3,4,5,7,9,10,12,and 13 were determined by single-crystal X-ray diffraction.In the solid state,all compounds comprised extensive hydrogen-bonded supramolecular networks.Representative studies of the energetic properties(impact and friction sensitivity,combustion)revealed that some of the new compounds can be classified as primary explosives.
