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Home , Fulminate, Pseudohalogen

CHEMISTRY OF PSEUDOHALIDES

Edited by ANDREJ M. GOLUB Faculty of Sevcenko-University Kiev USSR HELMUT KÖHLER Chemistry Department Martin-Luther-University Halle—Wittenberg GDR

and

VIKTOR V SKOPENKO Faculty of Chemistry Sevcenko-University Kiev USSR

ELSEVIER Amsterdam — Oxford — New York — Tokyo 1986 Contents

List ol important symbols 13

Introduction 16 The concept of . Pseudohalides, pseudohalogens 15 Nomenclature of derivatives 16 Characteristics of pseudohalides 17 Classification of the pseudohalogen compounds — bonding tendencies of the pseudohalides 23 References 26

Inorganic compounds 28 Survey of the binary nitrogen-hydrogen compounds 28 Hydrogen azide 28 1. Gaseous, liquid and solvent-free HN3 (azoimide) 28 2. Hydrazoic 30 Analytical and structural properties of the azide group 32 1. Bonding properties and structural considerations 32 2. Structure of the azide radical and nitrenes 36 3. Analytical chemistry of the azide compounds 37 Classification of 39 Azides of the s-elements 39 1. Alkali azides 39 2. Alkaline-earth azides 41 3. Properties of the alkaline-earth and alkali-metal azides 42 Azides of the p-elements 46 1. Azides of and semi-metals 46 2. Azides of , gallium, indium and thallium 61 3. , , antimony and bismuth azides 52 Azides of the subgroup elements 53 1. Azides of the elements of the subgroups I and II 54 2. Azides of the elements of the subgroups III to VII 57 3. Azides of the elements of subgroup VIII 59 Application of the azides 61 References 64

Cyanides 77 Preparation and properties of 77 Hydrogen 79 1. Properties of 79 2. Preparation and structure of hydrogen cyanide 80 3. Reactions of hydrogen cyanide 81 Ammonium, alkali and alkaline-earth 81 1. Preparation of alkali and alkaline-earth cyanides 82 2. General properties of ionic cyanides 82 10 Contents

3.4. Electronic structure and complex formation ability of the cyanide .... 85 3.5. Cyano compounds of the p- and d10-elements 87 3.5.1. Binary cyanides 87 3.5.2. Anionic cyano complexes of the p- and d10-elements 92 3.6. Cyanides and cyano complexes of the transition metals 96 3.6.1. Cyano compounds of the metals of subgroup I 97 3.6.1.1. Metal cyanides 97 3.6.1.2. Metal cyano complexes 97 3.6.2. Cyanides of the metals of subgroup III 103 3.6.2.1. Cyanides of the Ianthanoeides 103 3.6.2.2. Cyanides of the actinoides 104 3.6.3. Cyano complexes of the metals of subgroup IV 105 3.6.4. Cyanides of the metals of subgroup V 105 3.6.5. Cyano compounds of the metals of subgroup VI 108 3.6.6. Cyano compounds of the metals of subgroup VII 113 3.6.7. Cyano compounds of the metals of the iron group 117 3.6.7.1. Binary metal cyanides 117 3.6.7.2. Cyano complexes 118 3.6.8. Cyano compounds of the platinum metals 130 3.6.8.1. Binary metal cyanides 130 3.6.8.2. Cyano complexes 130 3.7. Formation of cyano complexes in non-aqueous media 135 3.7.1. Cyano complexes of the metals of subgroups I and II 135 3.7.2. Cyano complexes of the metals of the iron group 139 3.7.3. Investigation of cyanides 139 3.7.4. Investigation of cyano complexes in salt melts 140 3.8. Structural analysis of cyano complexes 142 3.8.1. Use of vibrational spectroscopy in the structural analysis of the cyanide com­ plexes 142 3.8.2. NMR-spectroscopic investigations of cyano complexes 147 3.8.3. X-ray structural analyses of the cyano complexes 147 3.9. Application of cyano compounds 155 3.9.1. Technical importance of covalent cyano compounds 155 3.9.2. Metal cyanides in the industry 161 3.9.3. Industrial application of cyano complexes 161 3.9.4. Cyanides in chemical analysis 162 3.9.5. Problems of cyanide disposal 163 3.10. References 164

4. and 186

4.1. Dioxycyanogen, (0CN)2 186 4.2. , structure and properties 187 4.3. Preparation and properties of ionic alkali, ammonium, and alkaline-earth cyanates 188 4.4. of the elements of the main groups III to VII 190 4.5. Cyanates of the d- and f-metals 195 4.6. 196 4.7. Metal fulminates 197 4.8. Structure and coordination tendency of the and . . . 198 4.9. Cyanate and complexes 200 4.9.1. Anionic compounds 200 4.9.2. Metal cyanate complexes with other 202 4.9.3. Reactions of the isocyanate complexes 207 4.10. Fulminate complexes 208 4.11. Structural analysis of cyanate and fulminate compounds 212 4.11.1. X-ray structural analyses 212 Contents 11

4.11.2. IR-spectroscopic investigations 217 4.11.2.1. IR-spectroscopic investigations of cyanate derivatives 218 4.11.2.2. IR-spectroscopic investigations of metal fulminates 223 4.11.3. NMR investigations of cyanate and fulminate complexes 227 4.12. Application of the cyanates and fulminates 228 4.13. References 230

5. compounds 239 6.1. Preparation and properties of dithiocyanogen 239 5.2. Hydrogen and isothiocyanic acid 241 5.3. of the s-metals and of ammonium 242 5.4. Preparation and properties of the thiocyanate compounds of the p- and d10- elements 244 5.4.1. Thiocyanates of metals of subgroup II 244 5.4.2. Thiocyanates of the elements of main group III 248 5.4.3. Thiocyanates of the elements of main group IV 250 5.4.4. Thiocyanates of the elements of main groups V to VII 253 5.5. Thiocyanates of the transition metals 255 5.5.1. Thiocyanates of the metals of subgroup 1 255 5.5.2. Thiocyanates of the rare-earth metals 259 5.5.3. Thiocyanates of the actinoides 261 5.5.4. Thiocyanates of the metals of subgroup IV 262 5.5.5. Thiocyanates of the metals of subgroup V 263 5.5.6. Thiocyanates of the metals of subgroup VI 265 5.5.7. Thiocyanates of the metals of subgroup VII 267 5.5.8. Thiocyanates of the metals of the iron group 270 5.5.9. Thiocyanates of the platinum metals 275 5.6. Characteristics of the complexing behaviour of the thiocyanate ion 276 5.7. IR-spectroscopic investigations and X-ray structural analyses of thiocyanate compounds 279 5.7.1. IR-spectroscopic investigations 279 5.7.2. Inversion of the coordination of the SON group 293 5.7.3. X-ray structural analyses 298 5.8. Application of inorganic thiocyanates 322 5.8.1. Thiocyanates in chemical synthesis 322 5.8.2. Thiocyanates in chemical analysis 323 5.8.3. Industrial applications of the thiocyanates 325 5.8.4. Environmental protection, biochemistry and medicine 327 5.9. References 328

6. Selenocyanate compounds 364 6.1. Diselenocyanogen and its properties 364 6.2. Analytics of the selenocyanate ion 365 6.3. Isoselenocyanic acid and its salts 365 6.4. Selenocyanates of the p- and d10-metals 369 6.5. Investigation of selenocyanate complexes in solution 370 6.5.1. Complex formation in aqueous and mixed solution 370 6.5.2. Methanolie solutions 372 6.5.3. Dimethylformamide solutions 373 6.5.4. Dimethylsulfoxide solutions 374 6.5.5. Acetone solutions 374 6.5.6. Solutions in acetonitrile 376 6.5.7. Influence of the solvent on the complexing reaction of selenocyanate 376 6.6. Coordination types of the selenocyanate 377 6.7. Coordination compounds of metal selenocyanates with amines 378 6.7.1. Compounds with pyridine and its derivatives 378 12 Contents

6.7.2. Compounds containing dipyridyl and phenanthroline 380 6.7.3. Selenocyanate complexes with other amines 386 6.8. Complexes with 0-donor neutral ligands 386 6.8.1. Compounds containing dimethyl sulfoxide and dimethyl formaldehyde .... 387 6.8.2. Compounds containing hexamethyl phosphorus triamide 389 6.8.3. Other selenocyanate complexes 391 6.9. Organometal selenocyanates and phosphine complexes of metal selenocyanates 393 6.10. Anionic selenocyanate complexes 394 6.10.1. Synthesis of the compounds 394 6.10.2. Anionic complexes with bridging SeCN groups 397 6.10.3. Anionic selenocyanate complexes 399 6.10.4. Anionic isoselenocyanate complexes 401 6.10.5. Mixed pseudohalogenometallates 404 6.11. References 406

7. Tricyanomethanides 413 7.1. The pseudohalide character of the tricyanomethanide ion 413 7.2. Properties and structure of the tricyanomethanide ion 414 7.3. Bond types of the tricyanomethanides and methods of their analysis 416 7.4. Covalent tricyanomethanides of the main group elements 419 7.4.1. Dicyanketenimine, HNCC(CN)2 419 7.4.2. Halogenotrieyanomethanes 420 7.4.3. Organometal tricyanomethanides 421 7.5. Tricyanomethanides of the d- and f-metals 424 7.6. Transition-metal tricyanomethanide complexes with other ligands 427 7.6.1. Complexes with N- and 0-donor 427 7.6.2. Complexes with C- and P-ligator molecules 430 7.7. References 432

8. Dicyanamides 434 8.1. The pseudohalide character of the dicyanamide ion 434 8.2. Properties and structure of the dicyanamide ion 436 8.3. Bond types and methods of their analysis 437 8.4. Dicyanamides of the p-elements 441 8.5. Dicyanamides of the d-metals 444 8.6. Dicyanamide complexes of the d- and f-metals 447 8.6.1. Complex formation in solution 447 8.6.2. Anionic complexes 447 8.6.3. Dicyanamide complexes with other ligands 450 8.7. References 453

9. Comparative characterization of the pseudohalides 455 9.1. Acidity and structure of the hydropseudohalic 455 9.2. of metal pseudohalides and metal halides 457 9.3. Ligand characteristics and donor activity of the pseudohalides 459 9.4. Mixed complexes of linear and non-linear pseudohalides 463 9.5. Further possibilities and tendencies in the chemistry of the pseudohalides . . 465 9.6. References 469

List of frequently used abbreviations 472

Subject index 476