Rhenium complexes sulfur

Thiiranes such as 2-methylthiirane and epithiocyclohexane, catalyzed by rhenium complexes, are useful reagents for sulfurization of phosphorus(iii) compounds (Equation (32) Table 3) <1997TL7701>. Mild reaction conditions and a short reaction time make this method of sulfurization of phosphorus(ni) compounds most interesting. Possible mechanisms for the rhenium-catalyzed sulfurization of phosphorus(lll) compounds are outlined in Scheme 38. 

Rhenium complex (46) is also known to add H2 and N2 <81CC451> to the metal center. Ruthenium complex (47) and osmium complex (48) add sulfur to give complexes with unusual S6 2 ligands <84AG(E)814>. 

Reported rhenium complexes possess one [70-74], two [75], and three [75] dithiocarboxylato ligands coordinated to the one rhenium atom to form a high coordination state, as in the case of the technetium complex [76]. One of these complexes 29 is synthesized from Re(VII)S4 and (PhCSS)2 (Fig. 10) [72]. An internal redox reaction occurs and Re( VII) is reduced to Re(III) in the synthetic process. Addition of sulfur-abstracting reagents, Ph3P or Et4NCN, produces the heptacoordinate complex 30 with the neutral capped octahedron structure or... 

Larger rhenium complexes are also the subject of a number of publications. Reaction of an excess of thietane with the thietane complex fRe3(CX))jQ(p-H)3(p-cyclo-SCH2CH2CH2)] affords a number of ring-opening oligomerisation products from which sulfur containing macrocycles such as 12-S-4, 16-S-4 and 24-S-6 can be eliminated upon addition of pyridine . Addition of... 

Cp(CO)2Re(THF) forms the complex 105 upon reaction with thiophene (89JA8753, 910M2436). Similar species are known for 2- and 3-methyl-, 2,5-dimethyl, and tetramethylthiophene (91IC1417). Thiophene in 105 is S-coordi-nated, and the sulfur atom is pyramidal. Treatment of 105 with Fc2(CO)9 produces 106, where the thiophene ligand is bridge-coordinated via the sulfur atom to rhenium and four carbon atoms of the dienic system with iron (the coordination mode). The pyramidal nature of the sulfur atom is preserved. The -coordination of thiophene separates the dienic and sulfur counterparts of the ligand and decreases the TT-electron delocalization, which leads to the enhanced basicity of the sulfur atom. 

Rhenium(VI) complexes, 4,194 alkoxides, 4,196 amides, 4,194 amines, 4,199 carboxylates, 4,199 dimethylformamide, 4,199 dioxane, 4,198 halides, 4,195,199 2-hydroxypyridine, 4,199 imides, 4,194 magnetic behavior, 1,271 mixed sulfur-nitrogen compounds, 4,196 N heterocycles, 4,199 nitrides, 4,194 oxide halides, 4, 195 oxoanions,4,196 pyridine, 4,199 sulfates, 4,198 sulfur compounds, 4,196 tellurates, 4,198... 

Scheme 31 Synthesis of ruthenium and rhenium disulfido complexes by the use of (TMS)2S as a sulfur reagent...

Molybdenum metalworking, 17 10-11 Molybdenum mill products, 17 9-10 Molybdenum-nickel alloys, 17 102 Molybdenum ore, U.S. exports of, 17 3t Molybdenum oxidation states, 17 20 Molybdenum oxides, 17 38 Molybdenum pentachloride, 17 23 Molybdenum-rhenium alloys, 17 15 Molybdenum sulfide, poisons in representative reactions, 5 258t Molybdenum-sulfur complexes, molecular, 17 37... 

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