Molybdenum complex compounds

Other molybdenum(II) compounds of interest include the nitric oxide complexes Mo(NO)Cl3 and Mo(NO)(dtc)3, /n j -MoH2(dppe)2 where dppe = l,2-bis(diphenylphosphino)ethane and K4 Mo2(SO J -2H20. 

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). 

This is by far the most stable and best-known oxidation state for chromium and is characterized by thousands of compounds, most of them prepared from aqueous solutions. By contrast, unless stabilized by M-M bonding, molybdenum(III) compounds are sparse and hardly any are known for tungsten(III). Thus Mo, but not W, has an aquo ion [Mo(H20)g] +, which gives rise to complexes [MoXg] " (X = F, Cl, Br, NCS). Direct action of acetylacetone on the hexachloromolybdate(III) ion produces the sublimable (Mo(acac)3] which, however, unlike its chromium analogue, is oxidized by air to Mo products. A black cyanide,... 

Secondary amines can be added to certain nonactivated alkenes if palladium(II) complexes are used as catalysts The complexation lowers the electron density of the double bond, facilitating nucleophilic attack. Markovnikov orientation is observed and the addition is anti An intramolecular addition to an alkyne unit in the presence of a palladium compound, generated a tetrahydropyridine, and a related addition to an allene is known.Amines add to allenes in the presence of a catalytic amount of CuBr " or palladium compounds.Molybdenum complexes have also been used in the addition of aniline to alkenes. Reduction of nitro compounds in the presence of rhodium catalysts, in the presence of alkenes, CO and H2, leads to an amine unit adding to the alkene moiety. An intramolecular addition of an amine unit to an alkene to form a pyrrolidine was reported using a lanthanide reagent. 

Molybdenum co-factor (Moco), 77 33 Molybdenum complexes, 26 927-929, 949 Molybdenum(III) complexes, 17 26-27 Molybdenum compounds, 17 19-43 in advanced structural and heating materials, 17 38-39 in anticorrosion agents, 17 39 biological aspects of, 17 31-34 biological uses for, 17 39-40 biomedical uses for, 17 40 catalytic applications of, 17 38 chemistry of, 17 29-31... 

Mononuclear molybdenum(V) compounds, 77 23. See also MolybdenumCV) dinuclear complexes... 

The molybdenum complex 1 (342 mg, 0.45 mmol, 1%) is added to a mixture of dichloromethane (90 mL), 1-octene (5.0 g, 44.6 mmol) and styrene (9.29 g, 89.2 mmol). The resulting mixture is stirred at room temperature for 1 h and then filtered through a pad of silica gel. After rinsing with dichloromethane the combined filtrates are concentrated and the crude product is purified by column chromatography (silica gel). 7.9 g (94%) of the title compound is obtained as a colorless oil. 

Pertechnetate and molybdate are reduced in acetic acid media by p-thiocresol and form complex compounds. As mentioned above the technetitun compound can be extracted by chloroform. Since the blue molybdenum complex is insoluble in this solvent separation of technetium from molybdenum can be achieved " . 

Together with Schrock s molybdenum-imido compound 50 ° the ruthenium-phosphine complexes 51 and especially 52 developed by Grubbs " proved to be an outstanding achievement in the development of molecular catalysts for olefin metathesis reactions (Scheme 10). 

The electronic spectra of niobium(IV) and -(V) and zirconium(IV) complexes 126,127) have been reported but not interpreted. The spectrum of Nb(ethyl-dtp)4 is of particular interest since the compound is probably 8-co-ordinate. Discussion of the spectrum of binuclear molybdenum complexes 130,131) employed the molecular orbital model of Blake, Cotton and Wood for MO2O3LX complexes s). 

As described in many reviews, Trost and his co-workers have carried out a pioneering work on the molybdenum-and tungsten-catalyzed allylic alkylation of allylic esters regioselectivity of the reaction is often complementary to the palladium-catalyzed allylic alkylation. The first asymmetric version was disclosed by Pfaltz and Lloyd-Jones in 1995 (Equation (63)). They used a catalytic amount of a novel tungsten complex, prepared from [W(CO)3(MeCN)3] or [W(cycloheptatriene) (COIs] and optically active (diphenylphosphino)phenyloxazolines 57, for the allylic alkylation of 3-aryl-2-propenyl phosphate with dimethyl sodiomalonate to isolate the corresponding branched alkylated compounds as a major isomer with an excellent enantioselectivity (96% ee). Unexpectedly, 3-aryl-2-propenyl carbonates are shown to be unreactive. It is worth noting that an isostructural molybdenum complex does not promote the catalytic alkylation under the same reaction conditions. In contrast, Lloyd-Jones and Lehmann reported the stereocontrolled... 

Azo compounds can be oxidized to azoxy compounds by peracids425 or by hydroperoxides and molybdenum complexes.42h The mechanism is probably the same as that of 9-28.427... 

Monomeric non-oxo molybdenum(V) complexes have been isolated with nitride (N3 ), imide (NR2-) and amide (NRR -) ligands, which may act as models for intermediates in the degradation of dinitrogen in nitrogenase. However, no molybdenum(V) compounds are yet known which correspond to the diazenide or hydrazide analogues of the molybdenum(IV) complexes described in Section 36.4.2.3. 

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