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Nitrogen-RichEnergeticMaterials Nitrogen-Rich Energetic Materials Edited by Michael Gozin and Leonid L. Fershtat Editors AllbookspublishedbyWILEY-VCHarecarefully produced.Nevertheless,authors,editors,and Prof.MichaelGozin publisherdonotwarranttheinformation SchoolofChemistry containedinthesebooks,includingthisbook, FacultyofExactSciences tobefreeoferrors.Readersareadvisedtokeep TelAvivUniversity inmindthatstatements,data,illustrations, TelAviv6997801 proceduraldetailsorotheritemsmay Israel inadvertentlybeinaccurate. CenterforNanoscienceand Nanotechnology LibraryofCongressCardNo.:appliedfor TelAvivUniversity TelAviv6997801 BritishLibraryCataloguing-in-PublicationData Israel Acataloguerecordforthisbookisavailable fromtheBritishLibrary. CenterforAdvancedCombustion Science Bibliographicinformationpublishedby TelAvivUniversity theDeutscheNationalbibliothek TelAviv6997801 TheDeutscheNationalbibliotheklists Israel thispublicationintheDeutsche Nationalbibliografie;detailedbibliographic Prof.LeonidL.Fershtat dataareavailableontheInternetat RussianAcademyofSciences <http://dnb.d-nb.de>. N.D.ZelinskyInstituteofOrganic Chemistry ©2023WILEY-VCHGmbH,Boschstr.12, Leninskyprosp.47 69469Weinheim,Germany 119991Moscow Russia Allrightsreserved(includingthoseof translationintootherlanguages).Nopartof CoverImage: thisbookmaybereproducedinanyform–by ©videoduck/Shutterstock photoprinting,microfilm,oranyother means–nortransmittedortranslatedintoa machinelanguagewithoutwrittenpermission fromthepublishers.Registerednames, trademarks,etc.usedinthisbook,evenwhen notspecificallymarkedassuch,arenottobe consideredunprotectedbylaw. PrintISBN:978-3-527-34929-6 ePDFISBN:978-3-527-83262-0 ePubISBN:978-3-527-83263-7 oBookISBN:978-3-527-83264-4 CoverDesign: Wiley Typesetting Straive,Chennai,India v Contents Preface xi AbouttheEditors xv 1 ChemistryofPentazole 1 MingLu,PengchengWang,YuangangXu,andQiuhanLin 1.1 Introduction 1 1.2 SubstitutedPentazoles 1 1.2.1 Arylpentazoles(ArN ) 2 5 1.2.2 HeterocyclePentazoles 3 1.2.3 Benzylpentazole(BzN ) 3 5 1.2.4 OtherSubstitutedPentazoles 3 1.2.5 PolypentazolesClusters 4 1.3 StrategiesforthePreparationofcyclo-N − 5 5 1.3.1 UsingHigh-EnergyElectronstoCleavetheC—NBondinArN 6 5 1.3.2 CleavingtheC—NBondofArN UsingRedoxChemistry 7 5 1.3.3 Possible[3+2]ReactionofN −andN atHighPressure 8 3 2 1.4 ComplexesofMetalandcyclo-N − 9 5 1.4.1 MetalSaltsofcyclo-N −(0D) 9 5 1.4.2 Metal–InorganicFrameworks(MIFs)ofcyclo-N − 10 5 1.4.3 CoordinationPolymers 12 1.4.4 StructuralCharacterization 14 1.4.4.1 MSandNMRCharacterization 14 1.4.4.2 TopologyAnalysis 14 1.4.4.3 RamanandIRAnalysis 15 1.4.4.4 StabilityAnalysis 16 1.4.4.5 BondingStudy 18 1.4.4.6 DetonationProperties 21 1.5 cyclo-N −-BasedNonmetallicIonicSalts 25 5 1.5.1 Synthesis 25 1.5.2 Single-CrystalX-RayStructures 26 1.5.3 Properties 37 1.5.3.1 15NNMR 37 1.5.3.2 IRSpectrum 38 vi Contents 1.5.3.3 ThermalStability 38 1.5.3.4 Sensitivity 40 1.5.3.5 Density 40 1.5.3.6 HeatofFormationandDetonationPerformance 40 1.6 Conclusions 43 References 43 2 AromaticFused-Ring-BasedEnergeticCompounds 47 KangcaiWangandQinghuaZhang 2.1 Introduction 47 2.2 Fused-RingAromaticEnergeticCompounds 49 2.2.1 [5,5]-Bicyclic-Backbone-BasedEnergeticCompounds 49 2.2.2 [5,6]-BicyclicEnergeticCompounds 53 2.2.3 OtherMulticyclicEnergeticCompounds 63 2.3 Conclusions 68 References 69 3 AdvancesinComputationsofNitrogen-RichMaterials 73 LeiZhangandChuangYao 3.1 WhyComputationandWhatRoleItPlays? 73 3.2 WhyNitrogen-RichHEDMsandHowTheyWork? 74 3.3 AdvancesinComputationofFirst-GenerationNitrogen-Rich HEDMs 75 3.4 AdvancesinComputationofSecond-GenerationNitrogen-Rich HEDMs 81 3.5 AdvancesinComputationofThird-GenerationNitrogen-RichHEDMs: PolynitrogenMaterials 84 3.5.1 Nitrogen-RichHEDMsComposedofN + 85 3 3.5.2 Nitrogen-RichHEDMsComposedofN + 86 5 3.5.3 Nitrogen-RichHEDMsComposedofcyclo-N − 87 5 3.5.3.1 SynthesisandRelatedMechanismatAmbientandHigh Pressures 87 3.5.3.2 PentazoleCompoundswithNon-nitrogenStabilizer 88 3.5.3.3 ArgumentontheProtonationofcyclo-N −in(N ) (H O) (NH ) Cl 90 5 5 6 3 3 4 4 3.5.3.4 StabilizationMechanismofDual-Aromaticcyclo-N − 91 5 3.5.4 All-NitrogenClusterN 93 4 3.5.5 All-NitrogenClusterN 93 6 3.5.6 All-NitrogenCrystalsComposedofN 94 8 3.5.7 All-NitrogenCrystalsComposedofN 95 10 3.5.8 All-NitrogenHEDMswithCubicGaucheStructure 96 3.6 FinalRemarks 97 Acknowledgement 98 References 98 Contents vii 4 LaserIgnitionofEnergeticTransitionMetalComplexes 107 MaximilianWurzenberger,DanielShem-Tov,andJörgStierstorfer 4.1 Introduction 107 4.2 SynthesisofEnergeticCoordinationCompounds 116 4.3 SynthesisofEnergeticTetrazoleLigands 116 4.4 SynthesisEnergeticCoordinationComplexes 121 4.5 ExamplesofMolecularStructures 122 4.6 EnergeticPropertiesofLigandsandCorrespondingEnergetic CoordinationCompounds 122 4.7 UV–VisSpectroscopyofEnergeticCoordinationCompounds 128 4.8 StudiesofIgnitionMechanism 128 4.9 Conclusions 134 References 135 5 Energetic1,2,3,4-Tetrazines 139 AleksandrM.Churakov,MichaelS.Klenov,AlekseyA.Voronin,and VladimirA.Tartakovsky 5.1 Introduction 139 5.2 MethodsofSynthesisandReactivityof1,2,3,4-Tetrazines 141 5.2.1 1,2,3,4-TetrazineswithCarbonSubstituentsatNitrogenAtoms 141 5.2.2 Annulated1,2,3,4-TetrazineswithBridgeheadNitrogenAtoms 142 5.2.3 FullyUnsaturated1,2,3,4-Tetrazines 142 5.2.3.1 Annulated1,2,3,4-Tetrazines 142 5.2.3.2 1,2,3,4-Tetrazine1-OxidesandBenzotetrazine1-Oxides 143 5.2.3.3 1,2,3,4-Tetrazine1,3-Dioxides 144 5.3 NMRandX-rayStudies 164 5.4 ThermalStability 168 5.4.1 TheoreticalStability 168 5.4.2 HeatResistance 169 5.4.2.1 Non-annulated1,2,3,4-Tetrazine1,3-Dioxides(TDOs) 171 5.4.2.2 Benzo-1,2,3,4-Tetrazine1,3-Dioxides(BTDOs) 172 5.4.2.3 BTDOsAnnulatedwithTDORing 173 5.4.2.4 BTDOsAnnulatedwithTetraazapentaleneSystem 174 5.4.2.5 BTDOsAnnulatedwithFuroxanRing 174 5.4.2.6 Tetrazine-1,3-Dioxides(TDOs)AnnulatedwithFive-Membered Heterocycles 175 5.4.2.7 TDOsAnnulatedwithTetraazapentaleneSystems 175 5.4.2.8 TDOAnnulatedwithSix-MemberedHeterocycle 175 5.4.2.9 1,2,3,4-TetrazineswithTwoBridgeheadNitrogenAtoms 177 5.5 Applications 177 References 179 viii Contents 6 RecentAdvancesinChemistryofNitrogen-RichEnergetic PolymersandPlasticizers 189 MichaelGozinandLeonidL.Fershtat 6.1 Introduction 189 6.2 HeterocyclicEnergeticPolymersandPlasticizers 189 6.3 Nitrogen-RichEnergeticPolymersLackingTraditionalExplosophoric Groups 201 6.4 Azido-RichEnergeticPolymersandPlasticizers 202 6.5 AzidoFluoropolymers 216 6.6 AzidoPlasticizers 219 6.7 NitroGroupContainingPolymers 225 6.8 AromaticC-NO ContainingPolymers 230 2 6.9 Conclusions 234 References 234 7 TetrazoleEnergeticSaltsBasedonVariousExplosophores: RecentOverviewofSynthesisandEnergeticProperties 239 SairaManzoor,Qamar-un-nisaTariq,andJian-GuoZhang 7.1 Introduction 239 7.2 Tetrazole-BasedEnergeticSalts 241 7.2.1 SynthesisofNitro,Nitramino,orAzidoTetrazoleEnergeticSalts 242 7.2.2 SynthesisofAmino/Hydrazine-TetrazoleEnergeticSalts 263 7.2.3 SynthesisofTetrazoleN-oxideEnergeticSalts 266 7.2.4 SynthesisofBistetrazoleorBridgedBistetrazoleEnergeticSalts 269 7.3 ConclusionandFutureTrends 278 7.4 Cautions 280 Acknowledgments 280 References 280 8 PropertiesandApplicationofNitrogen-RichCompoundBTATz inLow-SignaturePropellants 285 JianhuaYi,ZhihuaSun,YiXu,ZhaoQin,ChangjianWang,BozhouWang, HuiLi,HaijianLi,ChaoChen,XiaoXie,andFengqiZhao 8.1 Introduction 285 8.2 SynthesisofBTATz 286 8.2.1 Experimental 286 8.2.2 Synthesisof3,6-Bis(3,5-Dimethylpyrazole)-1,2-Dihydro-1,2,4,5- Tetrazine(3) 286 8.2.3 Synthesisof3,6-Bis(3,5-Dimethylpyrazole)-1,2,4,5-Tetrazine(4) 287 8.2.4 SynthesisofBTATz(5) 287 8.3 StructureofBTATz 287 8.3.1 GeometricConfiguration 287 8.3.2 BondOrders 289 8.3.3 VibrationandInfraredSpectrum 289 8.4 PropertiesofBTATz 290