CHEMISTRY OF PSEUDOHALIDES

Transcription

1 CHEMISTRY OF PSEUDOHALIDES Edited by ANDREJ M. GOLUB Faculty of Chemistry 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

2 Contents List ol important symbols 13 Introduction 16 The concept of pseudohalogens. Pseudohalides, pseudohalogens 15 Nomenclature of pseudohalogen derivatives 16 Characteristics of pseudohalides 17 Classification of the pseudohalogen compounds bonding tendencies of the pseudohalides 23 References 26 Inorganic azide compounds 28 Survey of the binary nitrogen-hydrogen compounds 28 Hydrogen azide Gaseous, liquid and solvent-free HN 3 (azoimide) Hydrazoic acid 30 Analytical and structural properties of the azide group Bonding properties and structural considerations Structure of the azide radical and nitrenes Analytical chemistry of the azide compounds 37 Classification of azides 39 Azides of the s-elements Alkali azides Alkaline-earth azides Properties of the alkaline-earth and alkali-metal azides 42 Azides of the p-elements Azides of metalloids and semi-metals Azides of aluminium, gallium, indium and thallium Tin, lead, antimony and bismuth azides 52 Azides of the subgroup elements Azides of the elements of the subgroups I and II Azides of the elements of the subgroups III to VII Azides of the elements of subgroup VIII 59 Application of the azides 61 References 64 Cyanides 77 Preparation and properties of cyanogen 77 Hydrogen cyanide Properties of hydrogen cyanide Preparation and structure of hydrogen cyanide Reactions of hydrogen cyanide 81 Ammonium, alkali and alkaline-earth cyanides Preparation of alkali and alkaline-earth cyanides General properties of ionic cyanides 82

3 10 Contents 3.4. Electronic structure and complex formation ability of the cyanide ion Cyano compounds of the p- and d 10 -elements Binary cyanides Anionic cyano complexes of the p- and d 10 -elements Cyanides and cyano complexes of the transition metals Cyano compounds of the metals of subgroup I Metal cyanides Metal cyano complexes Cyanides of the metals of subgroup III Cyanides of the Ianthanoeides Cyanides of the actinoides Cyano complexes of the metals of subgroup IV Cyanides of the metals of subgroup V Cyano compounds of the metals of subgroup VI Cyano compounds of the metals of subgroup VII Cyano compounds of the metals of the iron group Binary metal cyanides Cyano complexes Cyano compounds of the platinum metals Binary metal cyanides Cyano complexes Formation of cyano complexes in non-aqueous media Cyano complexes of the metals of subgroups I and II Cyano complexes of the metals of the iron group Investigation of metalloid cyanides Investigation of cyano complexes in salt melts Structural analysis of cyano complexes Use of vibrational spectroscopy in the structural analysis of the cyanide complexes NMR-spectroscopic investigations of cyano complexes X-ray structural analyses of the cyano complexes Application of cyano compounds Technical importance of covalent cyano compounds Metal cyanides in the industry Industrial application of cyano complexes Cyanides in chemical analysis Problems of cyanide disposal References Cyanates and Fulminates Dioxycyanogen, (0CN) Isocyanic acid, structure and properties Preparation and properties of ionic alkali, ammonium, and alkaline-earth cyanates Isocyanates of the elements of the main groups III to VII Cyanates of the d- and f-metals Fulminic acid Metal fulminates Structure and coordination tendency of the cyanate and fulminate ions Cyanate and isocyanate complexes Anionic compounds Metal cyanate complexes with other ligands Reactions of the isocyanate complexes Fulminate complexes Structural analysis of cyanate and fulminate compounds X-ray structural analyses 212

4 Contents IR-spectroscopic investigations IR-spectroscopic investigations of cyanate derivatives IR-spectroscopic investigations of metal fulminates NMR investigations of cyanate and fulminate complexes Application of the cyanates and fulminates References Thiocyanate compounds Preparation and properties of dithiocyanogen Hydrogen isothiocyanate and isothiocyanic acid Thiocyanates of the s-metals and of ammonium Preparation and properties of the thiocyanate compounds of the p- and d 10 - elements Thiocyanates of metals of subgroup II Thiocyanates of the elements of main group III Thiocyanates of the elements of main group IV Thiocyanates of the elements of main groups V to VII Thiocyanates of the transition metals Thiocyanates of the metals of subgroup Thiocyanates of the rare-earth metals Thiocyanates of the actinoides Thiocyanates of the metals of subgroup IV Thiocyanates of the metals of subgroup V Thiocyanates of the metals of subgroup VI Thiocyanates of the metals of subgroup VII Thiocyanates of the metals of the iron group Thiocyanates of the platinum metals Characteristics of the complexing behaviour of the thiocyanate ion IR-spectroscopic investigations and X-ray structural analyses of thiocyanate compounds IR-spectroscopic investigations Inversion of the coordination of the SON group X-ray structural analyses Application of inorganic thiocyanates Thiocyanates in chemical synthesis Thiocyanates in chemical analysis Industrial applications of the thiocyanates Environmental protection, biochemistry and medicine References Selenocyanate compounds Diselenocyanogen and its properties Analytics of the selenocyanate ion Isoselenocyanic acid and its salts Selenocyanates of the p- and d 10 -metals Investigation of selenocyanate complexes in solution Complex formation in aqueous and mixed solution Methanolie solutions Dimethylformamide solutions Dimethylsulfoxide solutions Acetone solutions Solutions in acetonitrile Influence of the solvent on the complexing reaction of selenocyanate Coordination types of the selenocyanate ligand Coordination compounds of metal selenocyanates with amines Compounds with pyridine and its derivatives 378

5 12 Contents Compounds containing dipyridyl and phenanthroline Selenocyanate complexes with other amines Complexes with 0-donor neutral ligands Compounds containing dimethyl sulfoxide and dimethyl formaldehyde Compounds containing hexamethyl phosphorus triamide Other selenocyanate complexes Organometal selenocyanates and phosphine complexes of metal selenocyanates Anionic selenocyanate complexes Synthesis of the compounds Anionic complexes with bridging SeCN groups Anionic selenocyanate complexes Anionic isoselenocyanate complexes Mixed pseudohalogenometallates References Tricyanomethanides The pseudohalide character of the tricyanomethanide ion Properties and structure of the tricyanomethanide ion Bond types of the tricyanomethanides and methods of their analysis Covalent tricyanomethanides of the main group elements Dicyanketenimine, HNCC(CN) Halogenotrieyanomethanes Organometal tricyanomethanides Tricyanomethanides of the d- and f-metals Transition-metal tricyanomethanide complexes with other ligands Complexes with N- and 0-donor molecules Complexes with C- and P-ligator molecules References Dicyanamides The pseudohalide character of the dicyanamide ion Properties and structure of the dicyanamide ion Bond types and methods of their analysis Dicyanamides of the p-elements Dicyanamides of the d-metals Dicyanamide complexes of the d- and f-metals Complex formation in solution Anionic complexes Dicyanamide complexes with other ligands References Comparative characterization of the pseudohalides Acidity and structure of the hydropseudohalic acids Solubility of metal pseudohalides and metal halides Ligand characteristics and donor activity of the pseudohalides Mixed complexes of linear and non-linear pseudohalides Further possibilities and tendencies in the chemistry of the pseudohalides References 469 List of frequently used abbreviations 472 Subject index 476