Sulphides, Selenides, and Tellurides

Vinyl Sulphides, Selenides, and Tellurides.—This account is divided into sections covering the synthesis of vinyl sulphides and selenides, their reactions, and their uses in synthesis. 

A vinylsilane is a useful equivalent of ethylene, adducts with a sulphenyl chloride readily undergoing elimination. Another novel elimination approach, i.e. oxidative decarboxylation of 2-substituted 2-(methylthio)propionic acids, is brought about by treatment of the sodium salt of the acid with A-chlorosuccinimide. 

Synthesis from alkynes has been touched on in the foregoing discussion, and brief details of points of interest are included as part of ref. 319 (see also ref. 365). 

Syntheses of vinyl sulphides from dithioesters include the conversions MeCSSMe - ( /Z)-MeSCMe=CHCSSMe nd MejCBrCSSMe - (RO)2P- 

Kobayashi, T. Taguchi, T. Morikawa, T. Takase, and H. Takanashi, Tetrahedron Lett., 1980, 21, 1047. 

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Mills, K. C., Thermodynamic Data for Inorganic Sulphides, Selenides and Tellurides, Butterworth, London (1974)... 

Includes bibliographical references and indexes. Contents v. 1. Primary, secondary, and tertiary phosphines, polyphosphines, and heterocyclic organo-phosphorus(III) compounds—v. 2. Phosphine oxides, sulphides, selenides, and tellurides—v. 3. Phosphonium salts, ylides, and phosphoranes. 

Volume 2 covers phosphine oxides, sulphides, selenides and tellurides. 

XXXVIII Organotin sulphides, selenides, and tellurides (containing an Sn-X-Sn bond). 

H2S, H2Se, H2Te.—Hydrogen sulphide, selenide, and telluride are prepared by treating a sulphide, selenide, or telluride with dilute sulphuric or hydrochloric acid FeS... 

Complexes with S-Donor, Se-Donor, or Te-Donor Ligands. The interatomic distances and valence distributions in the chromium thiospinels have been reviewed.151 Several mixed-metal sulphides, selenides, and tellurides containing chromium(m) have been reported this year, as detailed in Table 2. 

Hartley, F. R., ed. The Chemistry of Organophosphorus Compounds, Vol. 2. Phosphine Oxides, Sulphides, Selenides and Tellurides. John Wiley Sons Chichester ... 

The last decade has seen an explosion of activity in the field as electrochemists have wrestled with unfamiliar, and often intractable, problems generated by the very wide range of materials investigated, difficulties often compounded by the use of polycrystalline samples whose bulk and surface properties have proved resistant to control. In addition to the elemental semiconductors and the III/V materials, a huge range of n- and p-type oxides, sulphides, selenides, and tellurides have been described and surface and bulk modifications carried out in the hope of enhancing photoelectrochemical efficiency. New theoretical and experimental tools have developed apace and our fundamental understanding of the semiconductor-electrolyte interface has deepened substantially. 

Thermodynamic Data for Inorganic Sulphides, Selenides and Tellurides,... 

Thermodynamic Data for Inorganic Sulphides, Selenides, and Tellurides," Butterworths, London, S. Heinel, J. G. Ehlers, and S. Gordon, Nat. Aero. Space Admin., NASA SP 3001, 1963. 

An alloy of a T metal with a B element of Gps. VB and VIB often has intermediate phases quite different from those of the constituent elements. They frequently have structures like NiAs (p. 149) examples are the arsenides, antimonides, bismuthides, sulphides, selenides and tellurides of many T metals. The binding is partly covalent and partly ionic. 

The structures of the sulphides, selenides and tellurides of the Gp. IIA metals illustrate the effect of the cation/anion size ratio on co-ordination number (Table 48). 

A large number of sulphides, selenides and tellurides have been made by heating the elements together in evacuated silica tubes, and by the thermal decomposition of the higher compounds. The solids have compositions represented by MX, MgXg, MXg, MX3 and MX4, not all the variants have been produced, and many of the phases are non-stoichiometic (p. 158). 

We may make two generalizations about crystalline metal halides. First, fluorides differ in structure from the other halides of a given metal except in the case of molecular halides (for example, Sbp3 and SbCl3 both crystallize as discrete molecules) and those of the alkali metals, all the halides of which are essentially ionic crystals. In many cases the fluoride of a metal has a 3D structure whereas the chloride, bromide, and iodide form crystals consisting of layer, or sometimes chain, complexes. (For exceptions, particularly fluorides MF3-MF5, see Table 9.9.) Second, many fluorides and oxides of similar formula-type are isostructural, while chlorides, bromides, and iodides often have the same types of structure as sulphides, selenides, and tellurides. The following examples illustrate these points ... 

Mills KC (1974) Thermodynamic data for inorganic sulphides, selenides and tellurides. Butterworths, London... 

Phosphine oxides have fallen upon hard times, judging by the current literature, which this year has provided fewer publications on the subject than were reviewed in the first volume of this series A timely reminder that the subject is nevertheless alive comes from the thorough reviews of phosphine oxides, sulphides, selenides, and tellurides in the new edition of Kosolapolf s compilation. These chapters are likely to be of particular value to chemists requiring a quick guide to known structures and their preparation. 

X 10 cm , and = 2.4lA obtained from a comparison of molecular properties of the sulphides, selenides, and tellurides of arsenic, antimony, and bismuth. These parameters were used by Uy and Drowart [69UY/DRO] in their calculation of the dissociation energy of BiSe(g) from mass-spectrometric measurements at high temperatures. 

Many of the oxides, sulphides, selenides and tellurides of the alkali metals (e.g. Li20, Li2S, etc.) have the so-called anti-fluorite structure, i.e. a fluorite structure in which the positions of the anions and cations are interchanged. Most of these can be regarded as essentially ionic compounds. The co-ordination is 4 8. 

I.r. spectra of some lanthanide disulphides have been measured and the presence of —S—S groups has been demonstrated. Values for the electron affinities of Se , and Te have been calculated as part of a study of the properties of alkaline-earth sulphides, selenides, and tellurides. Thermodynamic data for the sulphides of Fe, Co, and Ni have been related to the pH of their precipitation. The standard enthalpy of formation for the non-stoicheiometric sulphide Fe,, S has been deduced. Thermodynamic data for some lead chal-cogenides have been determined. ... 

Buketov EA, Ugoeets MZ and Pashinkin AS (1964) Solubility products and entropies of sulphides, selenides and tellurides. Russ J Inorg Chem 9 292-294. 

Sodium iodide, values of properties. See Alkali halides Sodium sulphide, selenide, and telluride. See Fluorites Soft-mode transition, 210... 

Mills [74M1L] has reviewed and selected thermochemical data for solid metal sulphides, selenides and tellurides and estimated an entropy value for ZrS2(cr) of ... 

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