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

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