Tungsten acetonitrile

Tricarbonylchromium,221 -molybdenum,221 -tungsten,221 and-ruthenium222 complexes of 1H-azepine-l-carboxylatcs have been prepared by treating the azepines with tris(acetonitrile)tricar-bonylchromium(O), tricarbonyldiglymemolybdenum(O), tris(acetonitrile)tricarbonyltung-sten(O), and dodecacarbonylruthcnium(O), respectively. 

Treatment of bis(pyridine) complexes of molybdenum and tungsten, M(f/ -allyl)Cl(CO)2(py)2 (M = Mo, W) with equimolar amounts of lithium amidinates Li[RC(NPh)2] (R = H, Me) afforded amidinato complexes of the type M(r -allyl)[RC(NPh)2](CO)2(py) (M = Mo, W). Reactions of the latter with acetonitrile, PEts, and P(OMe)3 have been investigated Free amidines react with M(r -allyl)Cl(CO)2(NCMe)2 according to Scheme 124 to give the corresponding bis(amidine) complexes. ... 

Kitatani et al. found that tungsten(VI) chloride would catalyse the formation of a range of oxazoles from benzoyl(phenyl)diazomethane and nitriles (Scheme 17).<74TL1531, 77BCJ1647> The reaction with acetonitrile was studied with a range of other metal chlorides, but all proved less satisfactory than WCle. They attributed the catalytic nature of tungsten(Vl) chloride to both its Lewis acidity and the affinity of tungsten for carbenes. 

Compound 79 reacts with 0(CH2)4 and NCMe in the presence of CFsSOsMe, like the iron complex 11 and the molybdenum and tungsten complexes 45 and 46, to give zwitterionic compounds [2-NO-2-PEt3-7-L-c/ow-2,l-CoCBioHio] [L = 0(CH2)4 (83), NCMe (84)]. Interestingly, the acetonitrile reaction gave in addition to 84 small amounts of the imine complex [7- N(Me) = C(H)Me -2-NO-2-PEt3-c/oio-2,l-CoCBioHio] (85), a product related to the iron and nickel compounds 34 and 78, respectively. The latter pair were the only products when 11 and 75, respectively, were... 

Irradiation of oxadisilirane 82c in an acetonitrile-methylene chloride solvent mixture in the presence of 9,10-dicyanoanthracene (DCA) as photosensitizer with a tungsten-halogen lamp under an oxygen flow resulted in the formation of 83c in 69% yield. In the absence of the sensitizer, no reaction occurred and 82c was recovered quantitatively. A similar result was also obtained in the reaction of 82c with 302 in the presence of 10 mol% of tris(p-bromophenyl)aminium hexachloroantimonate [ /j-BrCr,H/ (N+SbClfU (BPHA) as the single ET reagent, which gave 83c in 58% yield (Table 17)97. 

NftB2F 02WC,H,2, Tungsten(II), tetrakis-(acetonitrile)dinitrosyl-cis-bis[tetrafluoroborate( 1 -)],... 

The dicarbonylbis( 4-l,3-cyclohexadiene)molybdenum(0) (9g) and tungsten (1 lg) complexes are formed only in moderate yields, photochemically. They are readily accessible, however, by thermal reactions of the respective tricarbonyltris(acetonitrile)metal(0) complexes (19) and lg (20). 

An unusual reaction of W111 with nitriles has been reported by Schrock et al. to provide metal a nitrido tungsten complex [46], Treatment of 98 with acetonitrile or benzonitrile provides the tungsten carbyne 99, along with the nitrido complex 100 (Eq. (37)). Additional studies resulted in the identification of reaction conditions that... 

Bis[dw-butyLphosphano] tellurium replaces norbornadiene, cycloheptatriene, acetonitrile, and dimethyl(methylene)oxosulfurane in chromium, molybdenum, and tungsten complexes. The P —Te compound acts as a bidentate ligand with the two phosphorus atoms coordinated to the metal atom1. The tetracarbonylchromium complex [R = CH(CH3)J can be recrystallized without loss of tellurium2. 

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