Tungsten complex compounds

Anionic Complexes. Compounds of tungsten with acid anions other than haUdes and oxyhaUdes are relatively few in number, and are known only in the form of complex salts. A number of salts containing hexavalent tungsten are known. Potassium octafluorotungstate [57300-87-5] K WFg, can be prepared by the action of KI on W(CO)g in an IF medium. The addition of tungstates to aqueous hydrofluoric acid gives salts that are mostly of the type M(I)2(W2F. Similarly, double salts of tungsten oxydichloride are known. 

The only known trivalent tungsten complex is of the type M(I)2(W2Cl2). It is prepared by the reduction of strong hydrochloric acid solutions of K2WO4 with tin. If the reduction is not sufficient, a compound containing tetravalent tungsten, K2(WCl (OH)) [84238-10-0] is formed (57). 

Although distibenes, the antimony analogues of azo compounds, have never been isolated as free, monomeric molecules (130), a tungsten complex, tritungsten pentadecacarbonyl[p.2-Tj -diphenyldistibene] [82579-41-7] C2yH2Q025Sb2W2, has been prepared by the reductive dehalogenation of phenyldichlorostibine (131) ... 

Geometrical parameters provide much more information than simple identification. The phosphorus-carbon distance of 1.686(6) A in this tungsten complex is consistent with there being a double bond, as it is close to those observed in open chain phosphaalkenes. But how much better it would have been if the parent compound could have been studied uncomplexed, so that the strain in this unusual ring system could have been investigated. The geometrical parameters would then have provided very useful information about the likely reactivity of the compound, and information about the changes on... 

By far, the most W-Si bonds reported in the period that this review covers involve W(CO)n or (t]S-CsRs)W-containing compounds. A significant development has been that of a recyclable catalyst for the hydrosilylation of ketones the system begins with a polar liquid substrate (ketone or ester) and finishes with a non-polar liquid product (alkoxysilane). The rest state of the catalyst is a mixture of the [BlCgFsTH salts of 36 and 37 the tungsten complex is far more active than its molybdenum analog. 

The reaction of alkynyllithium compounds with alkoxycarbene tungsten complexes leads to anionic propargyl tungsten complexes (Figure 2.33 see also Figure 3.9). These intermediates are stable at low temperatures and react upon Lewis acid catalysis with aldehydes or A -sulfonyl imines to yield five-membered heterocycles [280]. Oxidative methoxycarbonylation [375] of the intermediate vinyl tungsten complex, followed by elimination of methanol leads to pyrroles or furanes (Figure 2.33 Entry 6, Table 2.22). 

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... 

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... 

The distorted pentagonal-pyramidal coordination has been identified also in Mo and W oxo diperoxo siloxane complexes64 (14-17). Crystal structures for species 14, 15 and 16 have been solved, while for the tungsten dinuclear compound, structural identification was suggested on the basis of similar IR and Raman spectra obtained for complexes 16 and 1764. 

A number of reactions between M2(OR)6 compounds and alkynes have been found to give alkylidyne compounds by a metathesis of the M=M and C=C bonds (see Sections 15.3.6.4) and evidence has been presented275 for an equilibrium between a ditungstatetrahedrane and a methyl-idyne-tungsten complex supported by BulO ligands (equation 72). 

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