Molybdenum complexes metal sulfides

SoHd lubricants ate added to help control high friction characteristics in high speed or heavy-duty appHcations where high temperatures are generated. Molybdenum disulfide [1317-33-5] M0S2, may be used alone or in a complex compound formed by grinding with fine natural graphite, and zinc sulfide [1314-98-3] ZnS. Other compounds include calcium fluoride, cryoHte [15096-52-3] Na AlF, rare-earth oxides, and metal sulfides, eg, iron, antimony, or zinc (see LUBRICATION AND LUBRICANTS). 

A catalytic asymmetric oxidation of mono-, di-, and tri-substituted alkenes using a chiral bishydroxamic acid (BHA) complex of molybdenum catalyst in air at room temperature leads to good to excellent selectivity. It has been suggested that the Mo-BHA complex combines with the achiral oxidant to oxidize the alkene in a concerted fashion by transfer of oxygen from the metal peroxide to the alkene.78 The chiral BHA-molybdenum complex has been used for the catalytic asymmetric oxidation of sulfides and disulfides, utilizing 1 equiv. of alkyl peroxide, with yields up to 83% and ees up to 86%. An extension of the methodology combines the asymmetric oxidation with kinetic resolution providing excellent enantioselectivity (ee = 92-99%).79... 

The molybdenum neopentyUdene complex Mo(CHBu )(NR)(OBu )2 is the active catalyst used in a fascinating development for the synthesis of 11-Vt semiconductor clusters (ZnS, CdS, PbS) and silver and gold nanoclusters of predictable size within microdomains in films of block copolymers prepared by ROMP. Block copolymers of norbomene and a functionalized norbomene that wiU complex with a metal-containing compound were prepared and characterized as monodisperse materials. The functionalized component (amine, alkoxide, or thiolate) then sequestered the metal and the metallated block copolymer was cast into a film which was subsequently treated with H2S to convert the metal into the sulfide. The molybdenum complexes have also featured in the development of the synthesis of side-chain liquid crystal polymers by living ROMP.98 99... 

Colona and coworkers oxidized a variety of alkyl aryl and heterocyclic sulfides to the sulfoxides using t-butyl hydroperoxide and a catalytic amount of a complex (97) derived from a transition metal and the imines of L-amino acids. Of the metals (M = TiO, Mo02, VO, Cu, Co, Fe), titanium gave the highest e.e. (21%), but molybdenum was the most efficient catalyst. The sulfoxides were accompanied by considerable sulfone125. 

The first thionitrosyl complex was discovered by chance during an attempted synthesis of molybdenum nitrido complexes in the presence of a source of sulfur, tetrathiuram sulfide.168 This work of Dilworth and Chatt was reported in 1974 and ultimately led to the syntheses of a range of Mo, Re and Os thionitrosyl complexes starting with the respective nitrido complexes.143,164 Nitrosyl complexes, like carbonyls, had been known for decades, and the more recent syntheses of thio-carbonyl complexes forebode the advent of thionitrosyl complexes. However, convenient synthetic routes based on analogies with syntheses of NO complexes were generally not available because the requisite precursors did not exist or were inconvenient to handle. Sulfiliminato complexes (M=N=SR2) of transition metals are as yet unknown. The chemistry of thionitrosyl complexes was the subject of a recent review.179... 

The flotation process is applied on a large scale in the concentration of a wide variety of the ores of copper, lead, zinc, cobalt, nickel, tin, molybdenum, antimony, etc., which can be in the form of oxides, silicates, sulfides, or carbonates. It is also used to concentrate the so-called non-metallic minerals that are required in the chemical industry, such as CaF2, BaS04, sulfur, Ca3(P03)2, coal, etc. Flotation relies upon the selective conversion of water-wetted (hydrophilic) solids to non-wetted (hydrophobic) ones. This enables the latter to be separated if they are allowed to contact air bubbles in a flotation froth. If the surface of the solids to be floated does not possess the requisite hydrophobic characteristic, it must be made to acquire the required hydrophobicity by the interaction with, and adsorption of, specific chemical compounds known as collectors. In separations from complex mineral mixtures, additions of various modifying agents may be required, such as depressants, which help to keep selected minerals hydrophilic, or activators, which are used to reinforce the action of the collector. Each of these functions will be discussed in relation to the coordination chemistry involved in the interactions between the mineral surface and the chemical compound. 

---