Sulphur, Selenium and Tellurium Derivatives

Mossbauer studies show RaSnXa poly(vinyl chloride) stabilizers to be converted into RaSnXCl where X=/jo-octylthio-glycollate or -maleate, and not the dichloride. A range of organotin dithiocarbamates has been prepared, monoalkyl being 7-co-ordinate, with bis(2-thio-5-nitropyridine)-5 -di-n-butyltin, 6-co-ordinate, and a 6-mercaptopurine riboside(5-,A-)tri-n-butyltin 5-co-ordinate. Dithiophosphate complexes are similarly 5- and 6-co-ordinate, with 

Barrau, M. Bouchaut, H. Lavayssiere, G. Dousse, and J. Satgd, Synth. React. Inorg. Metal-Org. Chem., 1980,10, 515 P. Jutzi, W. Steiner, and K. Stroppel, Chem. Ber., 1980, 113, 3357. 

The first open chain diorganotin sulphide (Pr 2SnS) has been formed by allowing the initially formed low molecular weight form to crystallize from DMF. A linear polymer crystallizes as a planar chain (90), and it appears that the stability of this form compared with the cyclic structure is determined mainly by the electronic effects of R rather than spatial requirements.  

Sulphur inserts into the vinyl-tin bond, as does tetracyanoethylene into the Sn—S bond of MeaSnSPh. A reinvestigation of the reaction of Mel with Mes-SnSMe shows MeaS+I and MegSnl to be the only products isolated. Aryl- 

Moedritzer, Inorg. Chim. Acta, 1978, 29,249 H. S. Dilanjan Soysa and W. P. Weber, Tetrahedron Letters, 1978, 235 P. Jutzi, W. Steiner, E. Konig, G. Huttner, A. Frank, and U. Schubert, Chem. Ber., 1978, 111, 606. 

Lavayssiere, G. Dousse, J. Barrau, J. Satg6, and M. Bouchaut, J. Organometallic Chem., 1978,161, C59 S. Sakai, H. Niimi, Y. Kobayashi, and Y. Ishii, Bull. Chem. Soc. Japan, 1977, 50, 3271. 

Bongartz, R. Sievers, and R. Zimmer, Angew. Chem. Internat. Edn., 1978, 17, 939. 

Pyrolysis of C-silyl substituted cyclopolysulphides at 400-600°c gives viSiMe CS2, iS2f thiophene, its homologues and silylated derivatives, while fragmentation of isomeric Me2s7cH CH SCH H2 and 

Me2SiCH2CH2SCHMe gives (Me2Si=S) as the most abundant ion. Spirobis ethylenedithia)silane has Si-S bonds of 211.6 pm, some 3.6 pm shorter than those of (Ph2Si 2S (SiSSi 112°). R SiSH (R=Bu 0) 

Thiosilanes cleave halogens from GaCl and SnCl2r and Rh2(CO) Cl2 

CH2CH2Si(OMe)3 for silica support].With (Me2Si)2S, (Ph2p)2MCl2 

PhLi/Te or Ph2Te2/Na with Me SiCl, and ring opens lactones, epoxides 

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Three earlier reviews cover thietanes and other derivatives up to the mid 1950s or 1960s Organic Compounds of Sulphur, Selenium and Tellurium, a Specialist Periodical Report of The Royal Society of Chemistry, includes reviews of smallring compounds (April 1969-March 1980 in six volumes). One chapter in Comprehensive Heterocyclic Chemistry gives a survey of four-membered sulfur hetero-cycles. A useful review on (2 + 2) cycloreversions covers some chemistry of relevance. ... 

The elements yield tetravalent derivatives m special circumstances, iu which they function as the basic elements. In the case of oxygen they are termed oxonium salts sulphur yields sulphonium salts whilst selenium and tellurium offer an even wider range of derivatives. Thus, the following types of compounds are now well known ... 

A method based on a similar principle was proposed for the determination of selenium in tellurium [155], A metal sample was dissolved in dilute (1 1) aqua regia to which an acidified solution of 4-phenyl-o-phenylenediamine was added. The resulting 5-nitro-piazelenol was determined chromatographicaUy on a column of SE-30 at 200°C with detection of the organic derivative of selenium by an electron-capture detector. Analogous methods were used for the analysis of selenium and mercury in pure sulphuric acid [156] and sea water [157]. 

The reactions of phosphorus-selenium compounds are frequently analogous to those of phosphorus-sulphur compounds, but the known chemistry of phosphorus-selenium compounds is comparatively small, and that of phosphorus-tellurium derivatives even more limited. 

General Properties of Compounds of Cobalt—Cobalt and the Halogens—Oxy-Halogon Derivatives—Cobalt and Oxygen—Cobalt and Sulphur—The Alums—Cobalt and Selenium, Tellurium, Chromium, and Molybdenum—... 

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