A group of new tetracoordinate mononuclear 2-(N-phenylformimino)pyrrolyl boron chelates[BX_(2){κ^(2)N,N′-NC_(4)H_(3)-2-C(H)[double bond,length as m-dash]N-C_(6)H_(5)}](X=F3;mesityl(2,_(4),_(6)-trimethylphenyl,Mes)4;...A group of new tetracoordinate mononuclear 2-(N-phenylformimino)pyrrolyl boron chelates[BX_(2){κ^(2)N,N′-NC_(4)H_(3)-2-C(H)[double bond,length as m-dash]N-C_(6)H_(5)}](X=F3;mesityl(2,_(4),_(6)-trimethylphenyl,Mes)4;C_(6)F_(5)5;X2=1,1′-biphenyl-2,2′-diyl_(6))and the related binuclear complex[(C_(6)F_(5))_(2)B{κ^(2)N,N′-NC_(4)H_(3)-2-C(H)[double bond,length as m-dash]N-C_(6)H_(4)-N[double bond,length as m-dash]C(H)-C_(4)H_(3)N-κ^(2)N,N′}B(C_(6)F_(5))2]7 were synthesised via metathetic exchange reactions of sodium 2-(N-phenylformimino)pyrrolyl with BF_(3)·Et_(2)O(_(3)),BMes_(2)F(_(4))and 9-chloro-9-borafluorene(6).展开更多
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
基金Fundação para a Ciência e a Tecnologia for financial support(Project PTDC/QUI-QIN/31585/2017)for fellowshipstoP.K.,A.I.R.,C.S.B.G.,B.F.andD.V.V.(SFRH/BPD/89167/2012,PD/BD/113535/2015–ChemMatPhD Program,SFRH/BPD/107834/2015,SFRH/BD/80122/2011,and SFRH/BD/81017/2011,respectively)Centro de Química Estrutural,BioISI-Biosystems&Integrative Sciences Institute,Instituto de TelecomunicaçÃes,LAQV-REQUIMTE,IBB-Institute for Bioengineering and Biosciences,UCIBIO-REQUIMTE,and acknowledgethe financial support of FundaçÃo para a CiÃncia e a Tecnologia for financial support(Projects UIDB/00100/2020 and UIDP/00100/2020,UIDB/04046/2020 and UIDP/04046/2020,UIDB/50008/2020,UIDB/50006/2020 and UIDP/50006/2020,UIDB/04565/2020,and UIDB/04378/2020 and UIDP/04378/2020,respectively).
文摘A group of new tetracoordinate mononuclear 2-(N-phenylformimino)pyrrolyl boron chelates[BX_(2){κ^(2)N,N′-NC_(4)H_(3)-2-C(H)[double bond,length as m-dash]N-C_(6)H_(5)}](X=F3;mesityl(2,_(4),_(6)-trimethylphenyl,Mes)4;C_(6)F_(5)5;X2=1,1′-biphenyl-2,2′-diyl_(6))and the related binuclear complex[(C_(6)F_(5))_(2)B{κ^(2)N,N′-NC_(4)H_(3)-2-C(H)[double bond,length as m-dash]N-C_(6)H_(4)-N[double bond,length as m-dash]C(H)-C_(4)H_(3)N-κ^(2)N,N′}B(C_(6)F_(5))2]7 were synthesised via metathetic exchange reactions of sodium 2-(N-phenylformimino)pyrrolyl with BF_(3)·Et_(2)O(_(3)),BMes_(2)F(_(4))and 9-chloro-9-borafluorene(6).
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.
