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
Addition of N-heterocyclic carbenes(L=1,3-di-tert-butylimidazol-2-ylidene(ItBu),1,3-di-iso-propyl-4,5-dimethylimidazol-2-yildene(IiPr_(2)Me_(2)),1,3-mesitylimidazol-2-yildene(IMes)and 1,3-di-(2,6-di-isopropylphenyl)im...Addition of N-heterocyclic carbenes(L=1,3-di-tert-butylimidazol-2-ylidene(ItBu),1,3-di-iso-propyl-4,5-dimethylimidazol-2-yildene(IiPr_(2)Me_(2)),1,3-mesitylimidazol-2-yildene(IMes)and 1,3-di-(2,6-di-isopropylphenyl)imidazol-2-yildene(IPr))to the iron half-sandwich complex[Cp’FeI]_(2)(Cp’=η^(5)-1,2,4-(Me_(3)C)_(3)C_(5)H_(2),1)forms the neutral,16VE adducts[Cp’FeI(L)](2–5)in moderate to excellent yields.These complexes were structurally characterised.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.
基金the financial support by the Deutsche Forschungsgemeinschaft(DFG)through the Emmy-Noether and the Heisenberg program(WA 2513/2 and WA 2513/6,respectively)。
文摘Addition of N-heterocyclic carbenes(L=1,3-di-tert-butylimidazol-2-ylidene(ItBu),1,3-di-iso-propyl-4,5-dimethylimidazol-2-yildene(IiPr_(2)Me_(2)),1,3-mesitylimidazol-2-yildene(IMes)and 1,3-di-(2,6-di-isopropylphenyl)imidazol-2-yildene(IPr))to the iron half-sandwich complex[Cp’FeI]_(2)(Cp’=η^(5)-1,2,4-(Me_(3)C)_(3)C_(5)H_(2),1)forms the neutral,16VE adducts[Cp’FeI(L)](2–5)in moderate to excellent yields.These complexes were structurally characterised.
