Radicals polysulfide anions

Abstract Inorganic polysulfide anions and the related radical anions S play an important role in the redox reactions of elemental sulfur and therefore also in the geobio chemical sulfur cycle. This chapter describes the preparation of the solid polysulfides with up to eight sulfur atoms and univalent cations, as well as their solid state structures, vibrational spectra and their behavior in aqueous and non-aqueous solutions. In addition, the highly colored and reactive radical anions S with n = 2, 3, and 6 are discussed, some of which exist in equilibrium with the corresponding diamagnetic dianions. 

These radicals are the basis for a complex sequence of reactions involving radicalization of ions and dimerization of radical ions, resulting in polysulfide anions (Sx ), e.g. ... 

In principle, deprotonation of any of the sulfanes gives polysulfide anions In practice, this route is not employed and rather fewer anions are known compared with the sulfanes. It was established last century that sulfur dissolves in basic media to give intensely colored (often blue) solutions. The well-known polysulfide solution [NH4]2Sjt, which contains mostly X = 4 and 5, is obtained by bubbling H2S through a suspension of sulfur in ammonium hydroxide. It is accepted nowadays that the blue coloration of many of these solutions is a consequence of the 83 radical. This species has characteristic EPR, visible, and Raman spectra that have enabled its detection in a variety of solutions including liquid ammonia,DMF, and HMPA. 82 can be introduced as an impurity into alkali metal halides. In lapis lazuli (lazurite that is made synthetically as ultramarine blue Na8[Al68i6024]8 , n = 2-4), the blue color is due to the presence of 83 radicals, which has also been identified by Resonance Raman Spectroscopy ... 

NMR and visible spectra have established that a number of S-N anions are present in such solutions.The primary reduction products are polysulfides Sx, which dissociate to polysulfur radical anions, especially the deep blue 83 ion (/Imax 620nm). In a IM solution the major S-N anion detected by NMR spectroscopy is cycZo-[S7N] with smaller amounts of the [SSNSS] ion and a trace of [SSNS]. The formation of the acyclic anion 5.23 from the decomposition of cyclo-Sjl is well established from chemical investigations (Section 5.4.3). The acyclic anions 5.22 and 5.23 have been detected by their characteristic visible and Raman spectra. It has also been suggested that a Raman band at 858 cm and a visible absorption band at 390 nm may be attributed to the [SaN] anion formed by cleavage of a S-S bond in [SSNS]. ° However, this anion cannot be obtained as a stable species when [SsN] is treated with one equivalent of PPhs. 

Sulfur is known to be easily reducible in nonaqueous solvents and its reduction products exist at various levels of reduction of polysulfide radical anions (S . ) and dianions (Sm2 ) 173], Recently Be-senhard and co-workers [74] have examined the effect of the addition of polysulfide to LiC104-PC. Lithium is cycled on an Ni substrate with Qc=2.7 C cm 2 and cycling currents of 1 mA cm. The cycling efficiency in PC with polysulfide is higher than that without an additive. The lithium deposition morphology is compact and smooth in PC with added polysulfide, whereas it is dendritic in PC alone. 

The chemistry of polysulfide dianions is closely related to that of the radical-monoanions S since both types of anions are in equilibrium with each other in solution and in high-temperature melts, e.g. ... 

Ionic polysulfides dissolve in DMF, DMSO, and HMPA to give air-sensitive colored solutions. Chivers and Drummond [88] were the first to identify the blue 83 radical anion as the species responsible for the characteristic absorption at 620 nm of solutions of alkali polysulfides in HMPA and similar systems while numerous previous authors had proposed other anions or even neutral sulfur molecules (for a survey of these publications, see [88]). The blue radical anion is evidently formed by reactions according to Eqs. (5)-(8) since the composition of the dissolved sodium polysulfide could be varied between Na2S3 and NaaS with little impact on the visible absorption spectrum. On cooling the color of these solutions changes via green to yellow due to dimerization of the radicals which have been detected by magnetic measurements, ESR, UV-Vis, infrared and resonance Raman spectra [84, 86, 88, 89] see later. 

The chemistry of polysulfide radical anions S (n = 2-4) was reviewed by Chivers [12] in 1977, including a historical discussion describing the difficult route to the final identification of these ubiquitous and highly colored species. However, since that time considerable progress has been made. Only the species 82, 83, and S6 have been experimentally characterized in detail while the existence of 84 has only been suspected. The nature of the color centers in ultramarine-type solids (82 , 83 ) has been reviewed by Re-inen and Lindner [115]. 

The yellow disulfide radical anion and the briUiant blue trisulfide radical anion often occur together for what reason some authors of the older Hterature (prior to 1975) got mixed up with their identification. Today, both species are well known by their E8R, infrared, resonance Raman, UV-Vis, and photoelectron spectra, some of which have been recorded both in solutions and in solid matrices. In solution these radical species are formed by the ho-molytic dissociation of polysulfide dianions according to Eqs. (7) and (8). 8ince these dissociation reactions are of course endothermic the radical formation is promoted by heating as well as by dilution. Furthermore, solvents of lower polarity than that of water also favor the homolytic dissociation. However, in solutions at 20 °C the equilibria at Eqs. (7) and (8) are usually on the left side (excepting extremely dilute systems) and only the very high sensitivity of E8R, UV-Vis and resonance Raman spectroscopy made it possible to detect the radical anions in liquid and solid solutions see above. 

The red tetrasulfide radical anion 84 has been proposed as a constituent of sulfur-doped alkali hahdes, of alkah polysulfide solutions in DMF [84, 86], HMPA [89] and acetone [136] and as a product of the electrochemical reduction of 8s in DM80 or DMF [12]. However, in all these cases no convincing proof for the molecular composition of the species observed by either E8R, Raman, infrared or UV-Vis spectroscopy has been provided. The problem is that the red species is formed only in sulfur-rich solutions where long-chain polysulfide dianions are present also and these are of orange to red color, too (for a description of this dilemma, see [89]). Furthermore, the presence of the orange radical anion 8e (see below) cannot be excluded in such systems. 

More recently, 84 may have been identified by ESR spectroscopy of solutions of Li2S ( >6) in DMF at 303 K. The lithium polysulfide was prepared from the elements in liquid ammonia. These polysulfide solutions also contain the trisulfide radical anion ( 2.0290) but at high sulfur contents a second radical at g=2.031 (Lorentzian lineshape) was formed which was assumed to be 84 generated by dissociation of octasulfide dianions see Eq. (32) [137],... 

Sulfur dissolves in liquid ammonia to give intensely coloured solutions. The colour is concentration-dependent and the solutions are photosensitive. Several S-N anions are present in such solutions.76,77 The primary reduction products are polysulfides Sx2, which dissociate to polysulfur radical anions, notably the deep blue S3 ion. In a 1M solution, the major S-N anion is cyc/0-[S7N] with smaller amounts of 21 and a trace of 20.76... 

Obviously, in solution, 83 is not stable against oxidation. It is stable in the mineral lapis lazuli, and the industrial ultramarine blue pigment [28]. In these materials, the radical 83 is encapsulated in the -cages of the sodalite structure, which protects it against oxidation. In ultramarine pigments, another radical anion polysulfide, 82 , has been observed. 

It is supposed to originate from the dissociation of 84 . This dissociation is perhaps significant at high temperatures, like those of the synthesis of ultramarine pigments or those of doping of alkali halide crystals. 83 and 82 radicals have also been observed in the alkali halides doped with sulfur [30, 31]. Another radical anion polysulfide, 84 , has been identified, by EPR experiments, in solution in DMF, originating from the dissociation of 8g , which is the least reduced polysulfide in this solvent [32]. 

Therefore, a complete description of the redox properties of sulfur and polysulfides in classical organic solvents has been obtained on the following basis only 8g and the radical anions 8 are reducible and only the dianions 8 and 8g are oxidable. The electrochemical process has been validated in DMF by comparing simulations and the experimental data in a wide range of temperatures (233 to 313 K) and scan rates (0.005 to 2.0 Vs ). It can be reasonably extended to other organic solvents. Thermodynamic and kinetic parameters have been discussed in Ref. 60. It must be noted that Paris et al. [58] describe the reduction of sulfur... 

Sulfur forms a series of homoatomic dianions catena-S (x = 2-8), which, without exception, have unbranched chain structures in the solid state.The electrochemical reduction of cyclo-Sg in aprotic solvents occurs via an initial two-electron process to produce catenaS P In solution, catena- and other long-chain polysulfides, e.g. catena- and catenaSi, dissociate via an entropy-driven process to give radical anions S (x = 2-4), including the ubiquitous trisulfur radical anion (x = 3). This intensely blue species is the chromophore in the mineral lapis lazuli, which is used in the manufacture of jewellery. 

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