دانلود کتاب Chalcogen-nitrogen chemistry : from fundamentals to applications in biological, physical and materials sciences

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Contents Preface: Updated Edition Preface: First Edition Acknowledgements About the Authors Chapter 1 Introduction 1.1 General Considerations 1.2 Binary Species 1.2.1 Neutral molecules 1.2.2 Cations 1.2.3 Anions 1.3 Cyclic Chalcogen Imides 1.4 Organic Derivatives 1.4.1 Acyclic systems 1.4.2 Chains and polymers 1.4.3 Cyclic systems 1.5 Ligand Chemistry and Metal Complexes 1.5.1 Neutral chalcogen-nitrogen ligands 1.5.2 Metal complexes of chalcogen-nitrogen anions 1.6 Chalcogen-Nitrogen Compounds with the Chalcogen in Higher Oxidation States 1.6.1 Acyclic systems 1.6.2 Cyclic systems 1.7 Content and Objectives of Updated Edition Books Book Chapters and Reviews Chapter 2 Formation of Chalcogen-Nitrogen Bonds 2.1 From Ammonia and Ammonium Salts 2.2 From Amines 2.3 From Amido-Lithium or Sodium Reagents 2.4 From Silicon-Nitrogen and Tin-Nitrogen Reagents 2.5 From Azides 2.5.1 Inorganic chalcogen-nitrogen compounds 2.5.2 Carbon-nitrogen-chalcogen compounds 2.6 From Nitriles References Chapter 3 Applications of Physical Methods 3.1 Diffraction Techniques 3.1.1 X-ray diffraction 3.1.2 Electron diffraction 3.2 14N and 15N NMR Spectroscopy 3.3 77Se and 125Te NMR Spectroscopy 3.4 Electrochemical Reduction and EPR Spectroscopy 3.4.1 Neutral radicals 3.4.2 Radical anions: SEEPR spectra 3.5 Photoelectron Spectroscopy 3.6 UV-Visible Spectroscopy 3.7 Infrared and Raman Spectroscopy 3.8 Mass Spectrometry 3.8.1 Electron impact (ionisation) mass spectrometry 3.8.2 Electrospray ionisation mass spectrometry 3.8.3 Laser desorption ionisation mass spectrometry References Chapter 4 Electronic Structures 4.1 Introduction 4.2 Hückel (4n + 2)p-electron Rule 4.3 Aromaticity 4.4 Thermodynamic Stability and Kinetic Inertness 4.5 Diradical Character 4.6 Electronegativity Effects 4.7 Bonding in the Polymer (SN)x and in Sulfur-Nitrogen Chains 4.8 Bonding in Heterocyclothiazenes 4.8.1 Isolobal analogy 4.8.2 Cycloaddition reactions 4.9 Weak Chalcogen-Chalcogen Interactions 4.9.1 Tetrasulfur tetranitride 4.9.2 Eight-membered phosphorus(III)- and phosphorus(V)-nitrogen-sulfur rings 4.9.3 Eight-membered carbon-nitrogen-sulfur rings 4.10 Radical Dimerisation: Pancake Bonding References Chapter 5 Binary Chalcogen-Nitrogen Neutral Molecules, Cations and Anions 5.1 Introduction 5.2 Neutral Molecules of the Type (NE)n (E = S, Se; n = 1, 2, 4, x) 5.3 Thiazyl, Selenazyl and Tellurazyl Monomers, NE (E = S, Se, Te) 5.3.1 Structure and spectroscopic characterisation 5.3.2 Metal complexes 5.4 Disulfur and Diselenium Dinitride, S2N2 and Se2N2 5.4.1 Structure and spectroscopic characterisation 5.4.2 Polymerisation 5.4.3 Adduct formation 5.5 Tetrasulfur and Tetraselenium Tetranitride, S4N4 and Se4N4 5.5.1 Preparation, properties and structure 5.5.2 Adduct formation 5.5.3 Reactions 5.6 Chalcogen-rich Nitrides 5.6.1 Nitrogen disulfide and diselenide, NS2 and NSe2 5.6.2 Trisulfur dinitride, S3N2 5.6.3 Tetrasulfur dinitride, 1,3-S4N2 5.7 Nitrogen-rich Chalcogen Nitrides 5.7.1 The isomers NNS and NSN 5.7.2 Thiatetrazole, SN4 5.7.3 Dithiatetrazine, S2N4, and trithiatetrazepine, S3N4 5.7.4 Pentasulfur hexanitride, S5N6 5.7.5 Nitrogen-rich selenium nitrides 5.7.6 Tellurium nitrides 5.7.7 Selenium and tellurium azides 5.8 Chalcogen-Nitrogen Cations 5.8.1 Thiazyl cation, [SN]+ 5.8.2 Dithianitronium cation, [SNS]+ 5.8.3 Dithiatriazyl cation, [S2N3]+ 5.8.4 Trichalcogenadiazyl cations [E3N2]+•, [E6N4]2+ and [E3N2]2+ (E = S, Se) 5.8.5 Cyclotrithiazyl cation, [S3N3] + 5.8.6 Cyclothiotrithiazyl [S4N3] +, cyclotetrathiazyl [S4N4] 2+and cyclopentathiazyl [S5N5] + cations 5.8.7 Tetrasulfur pentanitride cation, [S4N5] + 5.9 Chalcogen-Nitrogen Anions 5.9.1 Sulfur diimide dianion, [NSN]2– 5.9.2 [NS2] – anion 5.9.3 [SSNS] – anion 5.9.4 [SSNSS] – anion 5.9.5 Sulfur-nitrogen anions in sulfur-liquid ammonia solutions 5.9.6 [S2N2H] – anion 5.9.7 Metal complexes of acyclic sulfur-nitrogen anions 5.9.8 Trisulfur trinitride anion, [S3N3] – 5.9.9 Tetrasulfur pentanitride anion, [S4N5]– References Chapter 6 Short-Lived Chalcogen-Nitrogen Molecules: Matrix Isolation 6.1 Introduction 6.2 Sulfonyl Azides, XSO2N3 (X = F, Cl, CF3), and Sulfuryl Diazide, O2S(N3)2 6.2.1 Synthesis and structures 6.2.2 Applications 6.3 [NSO]•, [NSO2]•, [SNO]• and [SSNO]• Radicals 6.4 Conjugate Acids, HNSO and HNSO2 6.5 [H2NSO]•, syn- and anti-[HNSOH]• Radicals 6.6 Heterocumulene Radicals, [OCNSO]• and [OSNSO]• 6.7 Ternary S,N,P Molecules 6.8 Isomers of S2N2 6.9 Isomers of S4N4 References Chapter 7 Acyclic S,N,O Anions and S-Nitrosothiols: Role in Biological Signaling 7.1 Introduction 7.2 Thionyl Imide Anion, [NSO]– 7.2.1 Synthesis and structure 7.2.2 Metal complexes 7.3 [SSNSO]– Anion 7.4 Sulfuryl Imide, [NSO2]–, and Azidosulfite, [SO2N3]–, Anions 7.5 Thionitrite, [SNO]–, and Thionitrate, [SNO2]–, Anions 7.6 Thionitrous Acid, HSNO, and Isomers 7.6.1 Synthesis, structure, and spectroscopic properties 7.6.2 Detection 7.6.3 Transition-metal complexes 7.7 S-Nitrosothiols, RSNO 7.7.1 Synthesis 7.7.2 Solid-state structures and bonding 7.7.3 Spectroscopic properties 7.7.4 Transition-metal complexes 7.7.5 Reactions with nucleophiles and Lewis acids 7.8 Se-Nitrososelenols, RSeNO 7.9 Perthionitrite Anion, [SSNO]– 7.9.1 Synthesis and solid-state structures 7.9.2 Solution behaviour 7.9.3 The “Gmelin” reaction: Iron complexes of [SxNO] – (x = 1, 2) 7.10 Thiohyponitrite Dianion, [SN=NO]2– 7.11 NO/H2S Crosstalk 7.12 Conclusions References Chapter 8 Chalcogen-Nitrogen Halides: Synthetic Reagents 8.1 Introduction 8.2 Thiazyl Halides, NSX (X = F, Cl, Br) 8.2.1 Synthesis and structures 8.2.2 Reactions 8.2.3 Metal complexes 8.3 Thiazyl Trifluoride, NSF3 8.3.1 Synthesis and structure 8.3.2 Metal and Lewis acid complexes 8.3.3 Reactions 8.3.4 Synthetic applications of imidosulfur(VI) oxydifluorides 8.4 Acyclic Chalcogen-Nitrogen-Halogen Cations, [N(ECl)2]+ (E = S, Se) and [N(SeCl2)2]+ 8.5 Tellurium-Nitrogen Chlorides, [Te4N2Cl8]2+ and Te11N6Cl26 8.6 Thiodithiazyl and Selenadiselenazyl Dichloride, [E3N2Cl]Cl (E = S, Se) 8.7 Cyclotrithiazyl Halides, (NSX)3 (X = Cl, F) 8.8 Dihalocyclotetrathiazenes, S4N4X2 (X = Cl, F), and Cyclotetrathiazyl Fluoride, (NSF)4 8.9 Sulfanuric Halides, [NS(O)X]3 (X = Cl, F) 8.10 Chalcogen-Nitrogen Halides Containing Two Chalcogens 8.11 Imidochalcogen(II) Halides 8.12 Imidochalcogen(IV) Dihalides References Chapter 9 Cyclic Chalcogen Imides: From Five- to 15-Membered Rings 9.1 Introduction 9.2 Chalcogenylnitrosyls, RNE (E = S, Se) 9.3 Cyclic Sulfur Imides 9.3.1 Eight-membered rings 9.3.2 Six-, seven-, nine- and ten-membered rings 9.4 Cyclic Selenium and Tellurium Imides 9.5 Metal Complexes of Cyclic Chalcogen Imides References Chapter 10 Acyclic Organic Chalcogen-Nitrogen Compounds 10.1 Introduction 10.2 Organic Chalcogenylamines, RNEO (E = S, Se, Te) 10.2.1 Synthesis and structures 10.2.2 Synthetic applications 10.2.3 Metal complexes 10.3 N-Thiosulfinylamines, RNSS 10.4 Chalcogen Diimides, RN=E=NR (E = S, Se Te) 10.4.1 Synthesis 10.4.2 Structures 10.4.3 Cyclodimerisation and cycloaddition 10.4.4 Metal complexes 10.4.5 Redox behaviour 10.4.6 Synthetic applications 10.5 Diimidosulfinates, [RS(NR′)2]– 10.6 Triimidochalcogenites, [E(NR)3]2– (E = S, Se, Te) 10.7 Sulfur Triimides, S(NR)3, and Triimidosulfonates, [RS(NR′)3]– 10.8 Tetraimidosulfates, [S(NtBu)4]2–, and Tetraimidosulfuric Acid, H2[S(NtBu)4] 10.9 Chalcogen Diamides, Ex(NR2)2 (E = S, Se, Te; x = 1–4) 10.9.1 Synthesis 10.9.2 Structures 10.9.3 Reactions 10.10 Organochalcogen Azides and Nitrenes 10.11 Trisulfenamides, (RS)3N, and the Radical [(PhS)2N]• 10.12 Sulfimide, Ph2S=NH, and Monohalogenated Isomers, Ph2S=NX (X = Cl, Br) and Ph2FS≡N References Chapter 11 Diamagnetic Five-membered Carbon-Nitrogen-Chalcogen Rings: From Fundamentals to Functional Devices 11.1 Introduction 11.2 1-Chalcogena-2,5-diazoles and Benzo-2-chalcogena-1,3-diazoles 11.2.1 Synthesis 11.2.2 Structures 11.2.3 Lewis base (donor) properties 11.2.4 Lewis acid (acceptor) properties 11.2.5 Applications 11.3 1,2-Dithia-3-azolium Salts 11.4 1,2-Dichalcogena-3,5-diazolium Salts 11.5 1,3-Dithia-2,4-diazolium Salts 11.6 1-Thia-2,3,4-triazole-5-thiolate Salts References Chapter 12 Diamagnetic Six-, Seven- and Eight-membered Carbon-Nitrogen-Chalcogen Rings 12.1 Introduction 12.2 Benzo-1,3-dichalcogena-2,4-diazines 12.2.1 Synthesis 12.2.2 Molecular and electronic structures 12.2.3 Reactions 12.3 1-Chalcogena-2,4,6-triazinyl derivatives 12.4 1,5-Dithia-2,4,6-triazines 12.5 1,3,5-Trithia-2,4-diazines 12.6 1,3,5-Trithia-2,4-diazepines and Benzotrithiadiazepine Isomers 12.7 1,3,5-Trithia-2,4,6-triazepines 12.8 1,5-Dithia-2,4,6,8-tetrazocines 12.9 The 1,3,5-trithia-2,4,6,8-tetrazocine cation 12.10 Bicyclic Carbon-Nitrogen-Sulfur Ring Systems References Chapter 13 Paramagnetic Carbon-Nitrogen-Chalcogen Rings: Magnetic Materials 13.1 Introduction 13.2 Monocyclic and Resonance-Stabilised 1,2-Dichalcogena-3-azolyl Radicals 13.2.1 Synthesis 13.2.2 Molecular structures and properties 13.2.3 Reactions 13.2.4 Charge-transfer complexes 13.3 Monocyclic and Resonance-Stabilised 1,3-Dithia-2-azolyl Radicals 13.3.1 Synthesis 13.3.2 Molecular structures and properties: Bistability 13.3.3 Charge-transfer complexes 13.4 1,2-Dichalcogena-3,5-diazolyl Radicals 13.4.1 Synthesis 13.4.2 EPR spectra and electronic structures 13.4.3 Crystal structures 13.4.4 Properties and reactions 13.5 1,3-Dithia-2,4-diazolyl Radicals 13.6 1-Chalcogena-2,4,6-triazinyl Radicals 13.7 1,2,3-Trithia-4-azolium Radical Cations 13.8 2-Chalcogena-1,3-diazolyl Radical Anions 13.9 Radical Anions of Bicyclic 1-Chalcogena-2, 5-diazoles References Chapter 14 Metal Complexes of Carbon-Nitrogen-Chalcogen Radicals: Coordination Modes 14.1 Introduction 14.2 Transition-Metal Complexes of 1,2-Dichalcogena-3,5-diazolyl Ligands 14.2.1 Complexes of phenyl-1,2-dichalcogena-3,5-diazolyl radicals 14.2.2 Complexes of pyridyl-1,2-dichalcogena-3,5-diazolyl radicals 14.2.3 Complexes of pyrimidyl-1,2-dichalcogena-3, 5-diazolyl radicals 14.2.4 Complexes of furanyl-1,2-dichalcogena-3,5-diazolyl radicals 14.2.5 Complexes of benzoxalo-2-yl-1,2-dichalcogena-3,5-diazolyl radicals 14.2.6 Complexes of pyrimidyl-bis(1,2-dichalcogena-3,5-diazolyl) radicals 14.2.7 Complexes of benzo-1-thia-3-azolyl-1,2-dichalcogena-3,5-diazolyl radical 14.3 Lanthanide Metal Complexes of 1,2-Dichalcogena-3,5-diazolyl Ligands 14.4 Transition-Metal Complexes of 1-Thia-2,4,6-triazinyl Radicals 14.5 Lanthanide Metal Complexes of 1-Thia-2,4,6-triazinyl Radicals 14.6 Transition-Metal and Main Group Element Complexes of 1,3-Dithia-2-azolyl Radicals References Chapter 15 Secondary Bonding Interactions in Chalcogen-Nitrogen Compounds: Supramolecular Assemblies 15.1 Introduction 15.2 Intramolecular SBIs: Stabilisation of Reactive Functional Groups 15.2.1 Organo-selenium(II) and -tellurium(II) halides and azides 15.2.2 Organo-selenium(IV) and -tellurium(IV) trihalides 15.2.3 Organotellurium compounds with a Te=O functionality 15.2.4 Organo-selenium(II) and -tellurium(II) cations 15.2.5 Organotellurium(IV) cations 15.2.6 Solution behaviour 15.2.7 Electronic structures and bonding 15.3 Intermolecular SBIs: Supramolecular Chemistry 15.3.1 1-Chalcogena-2,5-diazoles 15.3.2 Benzo-2-chalcogena-1,3-diazoles 15.3.3 Iso-tellurazole N-oxides 15.3.4 Benzo-1,3-chalcogenazoles References Subject Index