Anion interaction dimethylsulfoxide

Solodovnikov (1976) studied the kinetics of the interaction of the 4-nitro-l-chlorobenzene with sodium methylate in dimethylsulfoxide in air via the method of spectrophotometry. Kinetic calculations were made in an assumption that all the anion radicals of 4-nitro-l-chlorobenzene are converted into 4-nitrophenolate. The calculations gave a sum of rate constants for formation of 4-nitroanisole and of the 4-nitro-l-chlorobenzene anion radicals close to the rate constant for the consumption of 4-nitro-l-chlorobenzene. Solodovnokov (1976) concluded that the anion radicals of 4-nitro-l-chlorobenzene are produced by a reaction parallel to substitution. Then it should be assumed that the reaction proceeds either by a nonradical mechanism or by a hidden radical mechanism, which implies that particles of a radical nature are produced and unite in a solvent cage without passing into a solvent pool. This conclusion generated objections (Shein 1983). The discussion deserves our consideration because it reveals features and limitations of the method for discerning the ion radical nature of a reaction. 

C6C15) with dimethylsulfoxide (DMSO), which leads to the synthesis of [Tl2 Au(C6F5)2 2 p-DMSO 3] or [Tl2 Au(C6Cl5)2 2 h-DMSO 2]ra, respectively.62 The crystal structure of the complex with fluorine shows a monodimensional polymer formed by repetition of [Au--Tl(p-0 = SMe2)3Tl] units, with gold-thallium interactions of 3.2225(6)-3.5182(8), while the pentachlorophenyl derivative contains two bridging DMSO molecules and an additional [Au(C6Cl5)2] anion. In addition, a thallium-thallium interaction of 3.7562(6) A appears in the latter (Fig. 21). 

Fig. 5 Solvent polarity dependence of the C-I- -Cl halogen bond association constants (log K, for the interaction of CgFiyl (red circles) and a tridentate anion receptor (blue squares). Solvents from left to right chloroform (e 4.81), dichlcnomethane (e 8.93), acetone (c 20.70), acetonitrile (e 37.5), and dimethylsulfoxide (e 46.70) [42]...

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