The inorganic heterocyclic chemistry of sulfur, nitrogen and phosphorus:
Gespeichert in:
1. Verfasser: | |
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Format: | Buch |
Sprache: | English |
Veröffentlicht: |
London [u.a.]
Acad. Press
1980
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Schlagworte: | |
Online-Zugang: | Inhaltsverzeichnis |
Beschreibung: | XV, 271 S. graph. Darst. |
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adam_text | The Inorganic Heterocyclic Chemistry
of Sulfur, Nitrogen and Phosphorus
HENRY G HEAL
The Queen s University of Belfast, Northern Ireland
ACADEMIC PRESS
A Subsidiary of Harcourt Brace Jovanovich, Publishers
London • New York • Toronto • Sydney • San Francisco
Contents
Preface
Chapter 1 Status, nomenclature, and methods of synthesis
I Introduction, 1
A Inorganic heterocycles: a modern perspective, 1
B The importance of inorganic heterocyclics, 3
II Nomenclature, 4
III Methods of synthesis, 8
A Introduction, 8
B Direct combination of the ring-forming elements, 9
C Addition polymerization, 9
D Heterofunctional condensations, 9
E Homofunctional condensations, 12
F Insertions, ring expansions, and ring contractions, 13
G Miscellaneous thermodynamically controlled processes, 14
H Controlled breakdown of pre-existing structures, 14
J Alteration of oxidation state of phosphorus or sulfur in existing
rings, 14
References, 15
Chapter 2 Cyclic sulfur imides with two-coordinate sulfur, and their derivatives
I Introduction, scope, and history, 16
II Linear amides of divalent sulfur, 18
III Sulfur imides based on the S8 ring, and their derivatives, 18
A Introduction, 18
B Monocyclic sulfur imides structurally related to cyclooctasulfur, 18
C Sulfur nitrides with coupled eight-membered, rings, 29
D The fused-ring sulfur nitride SnN2, 31
E The search for other fused-ring sulfur nitride ;, 33
* F Bis(heptasulfurimido) sulfoxide, S15N20, 33
G Polymeric sulfur nitride-imides: general, 34
H The conformational stability of saturated S-N rings, 35
X CONTENTS
IV Sulfur imides based on rings other than eight-membered, 36
A Introduction, 36
B Derivatives of six-membered ring imides, 36
C Derivatives of twelve-membered ring imides, 37
V Cyclic sulfur hydrazides, 37
A Eight-membered rings, 37
B Six-membered rings, 38
References, 38
Chapter 3 Imides and amides of sulfur(iv) as source materials for inorganic
heterocycles
I Introduction, 41
II Structural relationships, 41
III Thionyl imide and its derivatives, 43
A Thionyl imide, 43
B Thionyl imide polymers and isomer, 41
C Organic thionylimines, 46
D Trimethylsilyl sulfinylamine, 46
E Halogeno-thionylimines and bis(thionylimino)mercury, 47
F Bis(thionylimino)sulfur, 48
G Other thionyl imide substitution products with -NSO attached to
sulfur, 48
H The NSO ion, 49
IV Sulfur diimide and the sulfodiimides, 49
A Sulfur diimide, 49
B Organo-sulfodiimides, 49
C Bis(trimethylsilyl) sulfur diimide and monosilylated analogs, 50
D Bis(trimethylstannyl) sulfur diimide, 52
E Bis(trifluoromethyl sulfenyl) sulfur diimide, 52
F Halogeno-sulfodiimides, 52
V Amidosulfurous acid and its derivatives, M
A Introduction, 52
B Amidosulfurous acid and the ammonia-sulfur dioxide reaction, 53
C Imidodisulfurous acid and its salts, 54
D Organic derivatives of amidosulfurous acid, 55
E Amidosulfinyl halides, 55
VI Thionyl diamide and its derivatives, 56
A Thionyl diamide, 56
B Imidodisulfinamide, 56
C Organic derivatives of thionyl diamid;, 57
VII Alkyl and fluoroalkyl sulfimides as reagents for ring synthesis, 57
A Introduction, 57
B The sulfur imide Me2S = NSiMe3, 57
C Bis(trifluoromethyl)sulfimide (CF3)2S = NH, 57
VIII Mixed P-S rings containing sulfur(iv), 58
References, 58
Chapter 4 Imides and amides of sulfur(vi) as source materials for inorganic
heterocycles
I Introduction and structural relationships 60
CONTENTS xi
II Sulfamide and its derivatives: monomeric sulfimide, 62
A Introduction, 62
B Sulfamide, 63
C Metal derivatives of sulfamide, 64
D N-Halogenosulfamides, 65
E Organic derivatives of sulfamide and of monomeric sulfimide, 65
III Cyclic and linear polymers of sulfimide, 67
A Introduction, 67
B The preparation of cyclic and linear sulfimide polymers, 67
C Properties and derivatives of the cyclic sulfimides, 70
D Properties of the linear polymeric sulfimides, 71
E Four-membered sulfimide rings, 74
IV Mixed six-membered rings containing the sulfimide group, 74
A Introduction, 74
B The compound N3S304H, 74
C Preparation and properties of N3P2SCl402Me isomers, 75
D The cyclic anion 02S[NP(NH2)2]2N~, 75
V Mixed four-membered rings containing the sulfimide group, 76
A Introduction, 76
B The one-ring compound (MeN)2S02PF3, 76
C Spiro compounds, 76
VI Further imido derivatives of sulfur(vi), used or potentially usable in
heterocyclic synthesis, 77
A The S,S-dialkylsulfodiimides, 77
B The mercurial Hg[NS(0)F2]2, 79
References, 79
Chapter § Sulfanuric halides and related compounds
I Introduction: structural relationships, 81
II The sulfanuric halides, 83
A Preparation of the sulfanuric chlorides, 83
B Physical properties and structure of sulfanuric chlorides, 84
C The cyclic trimeric sulfanuric fluorides, 85
D The cyclic sulfanuric fluoride tetramer, 86
E High polymeric sulfanuric fluorides, 86
F Mixed sulfanuric chlorofluorides, 87
G Reactions and derivatives of the sulfanuric halides, 87
H The sulfanuric anion (N3S304F2)~, 89
J Isomerism of sulfanuric derivatives, 89
III Mixed sulfanuric rings wth other sulfur groups, 92
A Introduction, 92
B The anion N3S303F2 and compounds N3S3OLXF2 (X = F, CI), 92
C Preparation and properties of [NS(0)C1][NSCI]2 and [NS(0)C1]2
[NSC1], 93
D Preparation and properties of [NS(0)C1][NS02 |[NS], 93
IV Sulfanuric rings containing a saturated segment, 94
V Mixed sulfanuric-phosphazene rings, 94
A Introduction, 94
B Preparation and properties of [NS(0)C1][NPC12]2 and [NS(0)C1]2-
[NPC12], 94
Xll CONTENTS
C Preparation and properties of [NS(0)F]2[NPC12], 95
D Reactions and derivatives of the mixed sulfanuric-phosphazene
halides, 95
E The eight-membered ring [NPC12]3[NS(0)C1], 96
References, 96
Chapter 6 Formally unsaturated sulfur nitrides and sulfur nitride ions
I Introduction and plan of treatment, 98
II Thiazyl polymers, (SN)„, and thiazyl monomer, 99
A Tetrasulfur tetranitride, 99
B Disulfur dinitride, S2N2, 111
C Thiazyl polymer, (SN)*, 112
D Thiazyl monomer, SN, 114
III Other unsaturated sulfur-nitrogen ring molecules and ions, 114
A Introduction, 114
• B Tetrasulfur dinitride, S4N2, 115
C The thiotrithiazyl ion, S4N3 + , and its salts, 117
D The cyclopentathiazenium cation, S5N5 + , and salts, 120
E The S6N42+ cation and salts, 121
F The cations S3N2+ and S4N42 + , 122
G The cation S3N22 + , 123
H The anion S3N3~, 123
IV Sulfur-nitrogen cages based on tetrasulfur tetranitride, 123
A Introduction, 123
B The anion S4N5~, 124
C The cation S4N5 + , 124
D The sulfur nitride S5N6, 125
V Unsaturated non-cyclic ions, 125
A The thiazenium ion, SN + , 125
B The perthionitrate anion, NS4~, 125
References, 126
Chapter 7 Unsaturated cyclic sulfur nitride 5-halides and their ^-derivatives
I Introduction and history, 130
II Thiazyl halides (NSX)„, (NS)nX2, and (NS)3X, and their substitution
products, 131
A Thiazyl halides: general, 131
B Cyclo-(NSF)4 and cyclo-(NSCl)4; cyclo-(NS)iF2 and cyclo-(NS)4C!2,
C Cyclo-(NSF)3 and cyclo-(NSCl)3, 133
D The compound (NS)3Br2, 136
E The compounds (NS)3X (X = CI, Br, I), 136
F Monomeric thiazyl halides, 136
G Substitution products of the cyclic thiizyl halide oligomers, 137
III The sulfur nitride halides S3N2X2, 139
A Introduction and history, 139
B Preparation and properties of [S3N3CI] + C1~, 139
C Other compounds S3N2X2 (X = halogen) of unknown structure, 140
IV Covalent compounds containing the five-membei ed S3N2 ring, 141
A Introduction, 141
B Preparation of S3N2 derivatives, 141
CONTENTS xiii
C Properties of S3N2 derivatives, 142
D Structures of S3N2 derivatives, 143
V Sulfur-nitrogen halides of unknown structure, 143
References, 143
Chapter 8 Unsaturated cyclic sulfur nitride S-oxides and 5-oxide ions
I Introduction and history, 145
II Compounds with eight-membered S-N rings, 146
A S4N4O4, 146
B S4N402, 146
III Compounds with six-membered S-N rings, 148
A The ion S3N304~, 148
B The compound S3N302C1, 148
IV Compounds with five-membered S-N rings: the oxide S3N20, 148
V A sulfur nitride oxide ion based on the S4N4 cage: S4N50, 150
VI Sulfur nitride oxides of unknown structure, 150
References, 150
Chapter 9 Bonding and electron-counting in S-N heteroc ycles
I Introduction, 152
II S-N bond parameters in general, 153
A Length-force constant correlation, 153
B Length-order correlation, 153
C Energy-order correlation, 154
III Bond angles and lengths in formally saturated S -N rings, 156
A Configurations at nitrogen, 156
B Configurations at sulfur, 157
IV Bond lengths and angles in formally unsaturated S-N rings, 157
A Configurations at nitrogen, 157
B Configurations at sulfur, 159
V Synoptic treatments of bonding in unsaturated S-N heterocycles, 159
A Introduction, 159
B Aromaticity in near-planar rings, 159
C The cage or cluster viewpoint, 161
D Transannular bonding in general, 164
E Conclusion, 164
References, 165
Chapter 10 Phosphorus-sulfur rings and cages
I Introduction and history, 166
II Small-molecule phosphorus sulfides and derivatives, 167
A Preparation, characterization, and structure, 167
1 B Reactions, 172
C Uses of the phosphorus sulfides, 175
D The oxosulfide P4S604, 175
E Cage and ring compounds from halogenation of phosphorus sulfides,
III Organo-substituted P-S rings, 178
A Six-membered P3S3 rings, 178
B Five-membered P3S2 rings, 178
xiv CONTENTS
C Five-membered P4S rings, 179
D Four-membered P2S2 rings, 180
IV Phosphorus sulfide high polymers, 181
References, 182
Chapter 11 Saturated phosphorus-nitrogen heterocycles: the cyclo- and closo-
phosphazanes
I Introduction, 184
A Scope, status, and treatment, 184
B Conditions for stability of dimeric cyclophosphazanes, 186
II Saturated phosphorus(m)-nitrogen heterocycles, 137
A Introduction, 187
B Reactions of phosphorus trihalides with amines and ammonia, 188
C Cyclodiphosph(m)azanes: preparation, structure, and properties, 189
D Cyclotri- and cyclotetra-phosph(ni)azanes, 192
E Cage phosph(m)azanes: preparation structure and properties, 192
F Heterocyclic hydrazido derivatives of pnosphorus(m), 195
G Phosph(m)azane polymers, 196
III Saturated phosphorus(v)-nitrogen heteroc cles, 197
A Introduction, 197
B Reactions of phosphorus(v) halides wit h amines and ammonia, 197
C Cyclodiphosph(v)azanes: preparation, structure, and properties, 199
D Cyclophosph(v)azanes: trimers and higher oligomers, 205
E Spirophosph(v)azanes, 207
F Cage phosph(v)azanes, 208
G Heterocyclic hydrazido derivatives of phosphorus(v), 209
H Homologues of the cyclodiphosph(v)a/ anes with sulfonyl groups as
ring components, 210
IV The cage phosphazane-phosphazene anion Pi2N14Si26, 210
References, 211
Chapter 12 The phosphazenes
I General introduction, 214
II Literature, 215
III History, 216
IV General properties of the cyclic phosphazenes, 21
V Primary preparations of the cyclic phosphazenes, 217
A Introduction, 217
B Syntheses from ammonium halides and phosphorus(v) compounds, 218
C Synthesis from aminochlorophosphoranes, 221
D Oxidative phosphazene syntheses from phosphorus(m) halides, 221
E Other primary phosphazene syntheses, 221
VI Phosphazene polymers other than simple rings, 22 1
A Phosphazene high polymers, 221
B Linear phosphazene oligomers, 223
C Fused-ring, spiro, and coupled-ring phosphazene compounds, 224
VII Reactions and derivatives of the cyclic phosphazenes, 226
A Isomerism among substitution products of the eyclophosphazenes, 226
B Complexes with Lewis bases, 227
CONTENTS XV
C Nucleophilic substitution reactions of the phosphazenes: introduction,
D Halogen and pseudohalogen exchange, 228
E Nucleophilic substitution by -OH, -OR, -SR, 229
F Nucleophilic substitution by amino groups, 231
G Nucleophilic substitution by carbanions, 232
H Addition of phosphazenes to Lewis acids, including the proton, 234
J Catalytic arylation of phosphazenes, 237
K Reduction of phosphazenes, 237
VIII Molecular structure and its rationalization, 237
IX Electronic structure and the question of aromaticity, 242
References, 246
Chapter 13 Polymeric phosphorus nitrides and related compounds
I Introduction, 250
II History, 251
III The phosphorus nitrides and phospham, 251
A The gas-phase molecule PN, 251
B Amorphous phosphorus nitrides, including phosphorus mono-
nitride, (PN)*, 252
C Triphosphorus pentanitride, 253
D Phosphams, (PN2H)*, 254
IV Polymeric phosphorus oxonitride and thionitride 255
A Phosphorus oxonitride, (OPN)*, 255
B Phosphorus thionitride, (SPN)X, 256
V Desirable lines of work in this area, 256
References, 257
Appendix, 259
Index, 260
|
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publisher | Acad. Press |
record_format | marc |
spelling | Heal, Henry G. Verfasser aut The inorganic heterocyclic chemistry of sulfur, nitrogen and phosphorus Henry G. Heal London [u.a.] Acad. Press 1980 XV, 271 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Heterocyclic compounds Nitrogen compounds Phosphorus compounds Sulfur compounds Anorganisches Ringsystem (DE-588)4142572-8 gnd rswk-swf Phosphorheterocyclen (DE-588)4174425-1 gnd rswk-swf Stickstoffheterocyclen (DE-588)4183269-3 gnd rswk-swf Heterocyclische Verbindungen (DE-588)4159726-6 gnd rswk-swf Schwefelheterocyclen (DE-588)4180407-7 gnd rswk-swf Phosphorheterocyclen (DE-588)4174425-1 s DE-604 Stickstoffheterocyclen (DE-588)4183269-3 s Schwefelheterocyclen (DE-588)4180407-7 s Anorganisches Ringsystem (DE-588)4142572-8 s Heterocyclische Verbindungen (DE-588)4159726-6 s HEBIS Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=001488745&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
spellingShingle | Heal, Henry G. The inorganic heterocyclic chemistry of sulfur, nitrogen and phosphorus Heterocyclic compounds Nitrogen compounds Phosphorus compounds Sulfur compounds Anorganisches Ringsystem (DE-588)4142572-8 gnd Phosphorheterocyclen (DE-588)4174425-1 gnd Stickstoffheterocyclen (DE-588)4183269-3 gnd Heterocyclische Verbindungen (DE-588)4159726-6 gnd Schwefelheterocyclen (DE-588)4180407-7 gnd |
subject_GND | (DE-588)4142572-8 (DE-588)4174425-1 (DE-588)4183269-3 (DE-588)4159726-6 (DE-588)4180407-7 |
title | The inorganic heterocyclic chemistry of sulfur, nitrogen and phosphorus |
title_auth | The inorganic heterocyclic chemistry of sulfur, nitrogen and phosphorus |
title_exact_search | The inorganic heterocyclic chemistry of sulfur, nitrogen and phosphorus |
title_full | The inorganic heterocyclic chemistry of sulfur, nitrogen and phosphorus Henry G. Heal |
title_fullStr | The inorganic heterocyclic chemistry of sulfur, nitrogen and phosphorus Henry G. Heal |
title_full_unstemmed | The inorganic heterocyclic chemistry of sulfur, nitrogen and phosphorus Henry G. Heal |
title_short | The inorganic heterocyclic chemistry of sulfur, nitrogen and phosphorus |
title_sort | the inorganic heterocyclic chemistry of sulfur nitrogen and phosphorus |
topic | Heterocyclic compounds Nitrogen compounds Phosphorus compounds Sulfur compounds Anorganisches Ringsystem (DE-588)4142572-8 gnd Phosphorheterocyclen (DE-588)4174425-1 gnd Stickstoffheterocyclen (DE-588)4183269-3 gnd Heterocyclische Verbindungen (DE-588)4159726-6 gnd Schwefelheterocyclen (DE-588)4180407-7 gnd |
topic_facet | Heterocyclic compounds Nitrogen compounds Phosphorus compounds Sulfur compounds Anorganisches Ringsystem Phosphorheterocyclen Stickstoffheterocyclen Heterocyclische Verbindungen Schwefelheterocyclen |
url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=001488745&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
work_keys_str_mv | AT healhenryg theinorganicheterocyclicchemistryofsulfurnitrogenandphosphorus |