Metal sulfurization

With hot metals, sulfur dioxide usually forms both metal sulfides as well as metal oxides. In aqueous solution, sulfur dioxide is reduced by certain metals or by borohydrides to dithionites. 

Sulfur dioxide emissions may affect building stone and ferrous and nonferrous metals. Sulfurous acid, formed from the reaction of sulfur dioxide with moisture, accelerates the corrosion of iron, steel, and zinc. Sulfur oxides react with copper to produce the green patina of copper sulfate on the surface of the copper. Acids in the form of gases, aerosols, or precipitation may chemically erode building materials such as marble, limestone, and dolomite. Of particular concern is the chemical erosion of historical monuments and works of art. Sulfurous and sulfuric acids formed from sulfur dioxide and sulfur trioxide when they react with moisture may also damage paper and leather. 

Because of possible catalytic and biological relevance of metal-sulfur clusters, several such compounds of cobalt have been prepared. The action of H2S or M2S (M = alkali metal) on a non-aqueous solution of a convenient cobalt compound (often containing, or in the presence of, a phosphine) is a typical route. Diamagnetic [Co6Ss(PR3)6] (R = Et, Ph) comprise an octahedral array of metal atoms (Co-Co in the range 281.7 to 289.4pm), all faces capped by atoms,and show facile redox behaviour... 

Einschlag, m. striking (in), impact wrapper, envelope plait, fold woof admixture sulfur match (for casks) handshake, einschlagen, v.t. strike in, drive in break punch wrap up, cover follow, adopt dip (sheet metal) sulfur (wine). — v.i. sink in strike succeed shake hands, einschlagig, a. belonging, related, pertinent, appropriate. 

Synthesis from Compounds with Formal Metal-Sulfur... 

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]. 

Ryan RR, Kubas GJ, Moody DC, Eller PG (1981) Structure and Bonding of Transition Metal-Sulfur Dioxide Complexes. 46 47-100... 

Fig. 10. The putative transition-state complex formed between the Fe protein MgADP AlFj and the MoFe protein. For simplicity only one a/3 pair of subunits of the MoFe protein is shown. The polypeptides are indicated by ribbon diagrams and the metal-sulfur clusters and MgADP AlFi" by space-filling models (MOLSCRIPT (196)). The figure indicates the spatial relationship between the metal-sulfur clusters of the two proteins in the complex.

In the presence of the product ethylene during turnover the MoFe protein exhibits an EPR signal, with g values at 2.12, 1.998, and 1.987 129), which has been demonstrated to arise from FeMoco in an S = z spin state 130). However, direct interaction of the ethylene with the metal-sulfur cluster was not demonstrated. 

Fig. 1.2 Crystal structures of the major sulfides (metal atoms are shown as smaller or black spheres) (A) galena (PbS) structure (rock salt) (B) sphalerite (ZnS) structure (zinc blende) (C) wurtzite (ZnS) strucmre (D) pyrite structure and the linkage of metal-sulfur octahedra along the c-axis direction in (/) pyrite (FeSa) and (//) marcasite (FeSa) (E) niccolite (NiAs) structure (F) coveUite (CuS) structure (layered). (Adapted from Vaughan DJ (2005) Sulphides. In Selley RC, Robin L, Cocks M, Plimer IR (eds.) Encyclopedia of Geology, MINERALS, Elsevier p 574 (doi 10.1016/B0-12-369396-9/00276-8))...

Metal-Sulfur, -Selenium, and -Tellurium Bond Lengths, M—E—C Angles, and Torsion Angles for Three-Coordinate Aluminum, Gallium, and Indium Thiolates, Selenolates and Tellurolates", and Related Compounds... 

Stiefel, E. I. Matsumoto, K. Transition Metal Sulfur Chemistry Biological and Industrial Significances. ACS Symposium Series American Chemical Society Washington, DC, 1996, 653. 

Nitrogen oxide Metals Sulfur dioxide Metals... 

Hydrazinium nitrate Alone, or Metals Hydrogen sulfide Metals Potassium dioxide Metals Sulfuric acid Copper... 

See Ammonium nitrate Metals Chlorine Metals Chlorine trifluoride Metals Copper(II) nitrate Tin Fluorine Metals Iodine bromide Metals Iodine heptafluoride Metals Potassium dioxide Metals Sodium peroxide Metals Sulfur Metals Tellurium Tin... 

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