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The volume continues the description of acyclic sulfur - nitrogen compounds with sulfur having the oxidation number II and covers amino-di- and aminopolysulfanes as well as diamino-di- and diamino-polysulfanes. Numerous examples of the class of diamino-disulfanes and their interesting chemical properties are described: N, N'-disulfanediyl-bis(N-heterocycles), for instance, undergo S-S bond scission in a thermal or photochemical radical - dimer equilibrium or react with acetylenes to give thiophenes, and N, N'disulfanediyl-bis(phthalimide) is a sulfur transfer reagent for organic synthesis. The volume completes the series on sulfur - nitrogen compounds which is a unique and comprehensive source of information for this field in chemistry.
This volume treats the acyclic sulfur(II)-nitrogen compounds with one-coordinate and two-coordinate sulfur. Sulfur imide (S=NH) and N-organyl-sulfur imides (S=NR) are unstable compounds which can be stabilized by coordination to transition metals or trapped, for example, by Ä2 + 4Ü cycloaddition with 1,3-butadiene. Among dithionitryl (1+) salts, only ÄS=N=SÜ+AsF6- has been studied extensively. Cycloaddition with alkenes and triple bond compounds produce 1,3,2-dithiazolium salts. Thiohydroxylamine, HSNH2, has been detected in the gas phase. Numerous examples of N, N-diorganyl-amino-halogeno-sulfanes (XSNR2, X = F, Cl, Br, I; R = organyl) and salts of the cation (XS)2N+ (X = Cl, Br) are known. N, N-Diorganyl-amino-chloro-sulfanes are important synthetic reagents.
PF3, (CH3)3SiCl -> (CH3)3SiF, and RC(O)Cl -> RC(O)F. Others include the conversion of (C6H5)3P into (C6H5)3PF2 and of (R3NC(S)S)2 into R2NCF3, R=alkyl. In organic chemistry, fluorides are easily accessible from alcohols, geminal fluorides RR'CF2 from the respective aldehydes or ketones, and acyl fluorides RC(O)F from carboxylic acides by using DAST. Because DAST is easy to handle and gives clean reactions in syntheses, this Gmelin volume devotes much space to the description of the chemical and physical properties od DAST.
The present volume is the first of a series describing acyclic sulfur-nitrogen compounds with sulfur of oxidation number IV. The acyclic sw-N compounds are arranged according to the coordination number of the sulfur. Neutral compounds are described before ions and complex compounds. The preceding series "Sulfur-Nitrogen Compounds" Parts 2, 3, and 4 covers the cyclic sw-N compounds. In this volume, the first section deals with sulfur-nitrogen compounds with 1-coordinate sulfur and begins with the sulfur nitride {thiazyl) radical, SN. This transient molecule was observed in its electronic ground state and several electronically excited states. The descrip tions of the sulfur nitride (thiazyl) ...