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 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.
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) ions SN+ and SW follow. The SN+ ionwas studied in the gas phase as weil as in the solid state where it forms salts. Thionitrosyl complexes containing the SN Iigand as a terminal linear unit are described at the end of the first section. The second section concerns Sulfur-nitrogen compounds with 2-coordinate sulfur and starts with the description of poly(sulfur nitride), (SNlx· The preparation, crystal structure, and metallic and superconducting properties of (SN)x, which were extensively studied, fill a !arge part of the volume. Halogen-modified poly(sulfur nitride) such as the widely studied (SNBr )x 04 and Na-modified poly(sulfur nitride) are dealt with in the following chapters.
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) ions SN+ and SW follow. The SN+ ionwas studied in the gas phase as weil as in the solid state where it forms salts. Thionitrosyl complexes containing the SN Iigand as a terminal linear unit are described at the end of the first section. The second section concerns Sulfur-nitrogen compounds with 2-coordinate sulfur and starts with the description of poly(sulfur nitride), (SNlx· The preparation, crystal structure, and metallic and superconducting properties of (SN)x, which were extensively studied, fill a !arge part of the volume. Halogen-modified poly(sulfur nitride) such as the widely studied (SNBr )x 04 and Na-modified poly(sulfur nitride) are dealt with in the following chapters.
The present volume describes acyclic Sulfur-nitrogen compounds with sulfur of the oxida tion number II. The first chapter deals with sulfur imide (S=NH), N-organyl-sulfur imides (S=NR, R = or ganyl), and metal complexes of sulfur imides. N-Organyl-sulfur imides have not been isolated, but they can be trapped, for example, by cycloaddition and stabilized by coordination to transi tion metals. 11 The following chapter present a detailed survey of other 8 -N compounds with one coordinate sulfur, e.g., dithionitrous acid (S=N-SH) and derivatives, the salts of the dithionitryl ion (1 +) ([S=N=S]+), and N-thionitroso-diorganyl-amines (S=NNR , R = organyl). Only the reac 2 tions of [S=N=S]+ AsF5, among the known [S=N=S]+ salts, have been extensively studied. Cycloadditions with alkenes and triple bonded compounds produce 1 ,3,2-dithiazolium salts and their derivatives. S=NN(CH )z and S=NN(C H )z form transition metal complexes. The 3 6 5 Iigand is coordinated via the S atom in a monodentate manner.
This volume continues the description of acyclic sulfur(II)-nitrogen compounds with two-coordinate sulfur. N,N,N',N'-Tetraorganyl-substituted diaminosulfanes are generally prepared by reacting secondary amines with SCl2. N,N,N',N'-Tetraalkyl-diamino-sulfanes form adducts with boron compounds and complexes with transition metals. Carbon disulfide and various reagents of the X=C=Y type can be readily inserted into the S-N bonds. R2NSNR2 is reacted with CS2 to give R2NC(S)-Sn-C(S)NR2, n z 2. Reactions of R2NSNR2 with isocyanate and isothiocyanate, R'N=C=Y (Y = O,S), produce R2NSN(R')C(Y)NR2. The biological activity of diaminosulfanes with the appropriate substituents (e.g., R-OC(O), R = 2,2-dimethyl-2,3-dihydro-7-yl-benzofuran) has been explored.
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.
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.
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.
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) ions SN+ and SW follow. The SN+ ionwas studied in the gas phase as weil as in the solid state where it forms salts. Thionitrosyl complexes containing the SN Iigand as a terminal linear unit are described at the end of the first section. The second section concerns Sulfur-nitrogen compounds with 2-coordinate sulfur and starts with the description of poly(sulfur nitride), (SNlx· The preparation, crystal structure, and metallic and superconducting properties of (SN)x, which were extensively studied, fill a !arge part of the volume. Halogen-modified poly(sulfur nitride) such as the widely studied (SNBr )x 04 and Na-modified poly(sulfur nitride) are dealt with in the following chapters.
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