Polysulfide anions, structures

Batsanov et al. 23) reacted sulfur with PtCU and PtBr2 by heating mixtures of the reactants in evacuated, sealed ampoules. At 100 -200°C after 12-24 h, sulfide chlorides PtCljS (1.70 < x < 2 0.6 s y < 3.35) and sulfide bromides PtBr S (1.87 < x 2.06 0.84 y s 1.80) were formed. The compositions depended on the initial PtX2 S ratio, and the temperature. At 320-350°C, loss of chlorine led to the compounds PtClS (1.7 y 1.9). According to their X-ray powder patterns, all of these products retained the main structural features of the original platinum halides. From considerations of molar volumes, the authors deduced the presence of polysulfide anions. 

Interestingly, the sulfanes H2S are both proton acceptors and donors. In the first case sulfonium ions H3S are formed, in the second case hydrogen polysulfide anions HS are the result. While the latter have never been isolated in salts, several salts with sulfonium cations derived from the sulfanes with n = 1, 2, and 4 have been published. However, none of these salts has been structurally characterized by a diffraction technique. Therefore, the structures of the HsSn cations and HS anions are known from theoretical calculations only. 

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. 

The majority of polysulfide anions have acyclic structures. The configurations of S2 species are in accord with their bond valence (b) ... 

This area continues to provide many new compounds and structures, reflecting the versatility and thermodynamic stability of polysulfide anions. Most of the compounds are described under the appropriate metal elsewhere in the Encyclopedia, some of the most elegant recent developments have been with other p-block elements such as tellurium, bismuth, and antimony. ... 

A great variety of binary Mo-S complex anions is formed and can be isolated in reactions of the tetrathiomolybdate anion [MoS ] " with various suinde and polysulfide anions. The nature of the anionic products that can be isolated from these reactions depends on (a) the amount of excess sulfur used (and the types of ligands present in the reaction mixtures), (b) the type of counterion used in the isolation of the complex anions, and (c) the type of solvent employed in the synthetic procedure. In a recent article, we described a scheme that interrelates the various [Mo2(S),(S2)6-,] anions. In this scheme (Fig. 1), any of the six homologs can hypothetically be obtained from any other by either the addition of sulfur, or the abstraction of sulfur by triphenylphosphine. Experimentally, the correctness of this scheme has been verified by the successful synthesis of most of the [Mo2(S) (S2)6 ] complexes, or of their internal redox isomers. In the [Mo2(S), (82)6 series, the homologs with n = 4, 5, and 6 have been characterized structurally. Those with n = 2 and 3 have been characterized structurally as the internal-redox isomers, [(S4)Mo(S)(//-S)2(S)Mo S2)] (ref. 3) and... 

The thiosulfate by-product does not take part in the subsequent reactions with the organic chlorides. The x value in equation (160) is referred to as the rank of the sodium polysulfide a typical value for x is 2.25. However, since aqueous sodium polysulfide is a complex mixture containing various polysulfide anions in equilibrium, the final polymer obtained in equation (158) may contain various structural units -S - (n = 1 -4). In addition, the aqueous phase contains OH , resulting in some terminal OH groups in the polymer. By applying an excess of sodium polysulfide (1.3 mol per mol RCL), the number of chain-terminating OH groups is reduced (see equation 161). 

Consequently, sulfur dissolves in polysulfide solutions much faster than in equimolar monosulfide solutions [73]. In this context it is of interest that the analogous decaselenium dianion Scio has been prepared and structurally characterized in solid [PPN]2Seio [74]. This anion is however bi-cyclic. 

The red [SSNO] anion (37) is produced by the reaction of an ionic nitrite with elemental sulfur or a polysulfide in acetone, DMF or DMSO.115 The [SSNO] anion has a planar cis structure with a short S-S distance (1.99 A), and S-N and N-O distances of 1.67 and 1.22 A, respectively. The treatment of [SSNO]- with triphenylphosphine produces the thionitrite anion [SNO]- (38) with a bond angle of ca. 120° at nitrogen and S-N and N-O bond lengths of 1.69 and 1.21 A, respectively. 

The increasing importance of hypervalent 3-centre 4-electron bonding on going down Group 16 is reflected in the structures of Sej anions with n = 9-11, which are without parallel for the polysulfides. Although a chain structure is still apparent for the nonaselenide anion of [Sr(15-crown-5)2]Se936 (Figure 5a),... 

Compared with the huge number of oxo complexes only a few rhenium(V) compound with terminal sulfldo complexes are known. The square-pyramidal complex anion [ReS(S4)2] was first isolated in pure form in 1986 by a reaction of Rc207 with (Ph4P)Br and ammonium polysulfide in acetonitrile and the structure of the Ph4P+ salt has been elucidated. Later, the same complex anion was prepared from starting materials such as [Re2Cl8] , perrhenate, ... 

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. 

Sulfur-rich binary P-S anions of the type [S2P(p-S )2PS2] form monocyclic structures with sulfide or disulfide bridging units ( = 1, 2) (11.39). Another type of cyclic P-S anion with the general formula [(PS2) ] is formed in the reaction of white phosphorus with polysulfides in a non-aqueous medium these anions have homocyclic structures with two exocyclic sulfur atoms attached to each phosphorus atom, e.g. [P4Ss] (11.40). ... 

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. 

The S anion that forms in the first step is one of Several polysulfides (S -. Sj, Sj , Sfi-), all of which have open chain structures. The versatility of Cp2TiSj as a precursor to other rings and sulfur-carbon compounds is shown in Fig. 16.33. 

Copper(I) Sulfido Anions. There is a remarkable array of polynuclear anions containing sulfur rings or chains that can be isolated as salts of large cations. They are formed by dissolution of copper sulfides in polysulfide solutions or by the action of sulfur and H2S on ethanolic solutions of Cu11 acetate. Examples are ions such as [Cu2S20]4-, [Cu3Si2]3, and [Cu4Si8]4-. Many of the structures are quite complex, for example, (17-H-VII) and (17-H-VIII). 

From the reaction of Au with alkali metal polysulfide liquids, LiAuS and NaAuS were discovered. Both compounds contain infinite one-dimensional (AuS) chains, featuring alternating sulfide anions and linear coordinated Au centers. In LiAu8, the chains are zigzag and fully extended and they pack in mutually perpendicular sets. In NaAuS, the same chains coil in an unusual fashion so that they become interwoven to form layers reminiscent of chicken-wire (Figure 17). This novel coiling mode allows Au Au contacts to form, which help to stabilize the structure. 

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