Polysulfides structure types

Metal polysulfido complexes have attracted much interest not only from the viewpoint of fundamental chemistry but also because of their potential for applications. Various types of metal polysulfido complexes have been reported as shown in Fig. 1. The diversity of the structures results from the nature of sulfur atoms which can adopt a variety of coordination environments (mainly two- and three-coordination) and form catenated structures with various chain lengths. On the other hand, transition metal polysulfides have attracted interest as catalysts and intermediates in enzymatic processes and in catalytic reactions of industrial importance such as the desulfurization of oil and coal. In addition, there has been much interest in the use of metal polysulfido complexes as precursors for metal-sulfur clusters. The chemistry of metal polysulfido complexes has been studied extensively, and many reviews have been published [1-10]. 

The photoelectrochemical behavior of ZnSe-coated CdSe thin Aims (both deposited by vacuum evaporation on Ti) in polysulflde solution has been described by Russak and Reichman [112] and was reported to be similar to MIS-type devices. Specifically, Auger depth profiling showed the ZnSe component of the (ZnSe)CdSe heterostructures to convert to ZnO after heat treatment in air, thus forming a (ZnO)CdSe structure, while the ZnO surface layer was further converted to a ZnS layer by cycling the electrode in polysulfide electrolyte. This electrochemically generated ZnS layer provided an enhanced open-circuit potential compared to CdSe alone. Efficiencies as high as 5.4% under simulated AM2 conditions were recorded for these electrodes. 

Polyrotaxene complexes, 46 271-273 Polysilanes, mass spectra of, 18 251 Polysilazanes, preparation of, 6 265-272 Polysiloxanes, 42 149-150 Polysulfide metal complexes, 31 89-122 cluster structures, 31 96 compound types, 31 91-103 with coordinated polysulfide ligands, 31 91-97... 

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). ... 

Polysulfide Melt. Cl Sulfur Black 1 [1326-82-5] (Cl 53185), derived from 2,4-dinitrophenol, is the most important dye in this group which also includes the indophenol-type intermediates. The latter are applied in the stable leuco form. The derived dyes are usually confined to violet, blue, and green shades. Other members of this group are intermediates capable of forming quinoneimine (10) or phenazone structures (11) that produce red-brown or... 

The structures of nine of these compounds were determined by spectroscopic methods, while those of the 14 remaining materials were established by GC-MS only. The compounds can be classified into four types (A to D) the 1,2,4-trithiolanes (145-154), 1,2,4,5-tetrathianes (155-157), 1,2,3,5,6-pentathiepanes (158-163), which are all generally quite stable compounds, and the monoalkyl-substituted polysulfides (164-167), which tend to disproportionate into sulfur and disubstituted cyclic polysulfides. These compounds are structurally related to the cyclic polysulfide compounds reported from red alga Chondria californica in 1976 [136] and to compound 168 (3-hexyl-4,5-dithiacycloheptanone) reported from the brown algae of the Dictyopteris genus in 1971 [137]. The latter compound has more recently been found to be a potent inhibitor of bee venom-derived phospholipase A2 (PLA2) [138]. 

In the DEPT experiments, both peaks around 50 and 58 ppm are divided into three components and the levels of the protonation for these six individual resonances are evaluated. The peaks at 57.4, 58.0 and 58.6 ppm are assigned to the polysulfidic crosslinks in the Al, B1 and B2-type structures, respectively. The peaks at 37.2 and 50.7 ppm are due to Al-type polysulfidic crosslinks. There was no apparent structural match for the quaternary peak at 50.2 ppm. 

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 cross-links are composed of structures containing various sulfide lengths, usually described as monosulfidic, disulfidic, or polysulfidic, which are determined by the type, amoimt, and proportion of additives used in the rubber compoimd. 

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