Molybdenum complexes tungsten derivatives

Of the rather limited number of tetravalent molybdenum and tungsten derivatives known, wre shall mention here only molybdenum disulfide (M0S2), which occurs as the ore molybdenite and the octacyano complexes Mo(CN)i 4 and W(CN) 4 which, along with their pentavalent counterparts (p. 333), represent two of the very few examples of octa-covalency. 

Treatment of the complexes NMe4[Cr(CO)5) =C(0)Me ] with iodine in the presence of base and alcohols affords carboxylic acid esters in reasonable yield. Use of water or an amine in place of the alcohol provides the carboxylic acid or the amide. The molybdenum and tungsten derivatives... 

Molybdenum and tungsten hexacarbonyls are able to form anionic complexes (AsPli4)2[(OC)4M( -pz)2M(CO)4] upon reaction with sodium pyrazolate and PluAsCl (72CB3203). The cationic complexes [(rj -Cp)2Mo(/Lt-pz)2Mo(rj -Cp)2] " (n = 2, 3) are known as well (74HCA1988). The other representatives of the complexes containing an exobidentate ligand (26) are derived from 4//-pyrazoles [70ZAAC(379)169]. 

When methylene chloride was used as a solvent, it was found that 28 are obtained in minor amounts, while the dominating product is the -coordinated chloro-carbyne species [(> -Tp )Mo(CO)2(=CCl)], whose yield increases abruptly with substitution in the pyrazol-l-yl fragments (3-methyl-, 3,4,5-trimethyl-, and 3,5-dimethyl-4-chloro derivatives) [90AX(C)59,95JCS(D) 1709]. The tungsten analog can be prepared similarly. The chlorocarbyne molybdenum complex follows also from the reaction of the parent anion with triphenylsulfonium cation but conducted in dichloromethane. The bromo- and iodocarbyne derivatives are made similarly. 

The formation of rings that contain a thioether linkage does not appear to be catalyzed efficiently by Ru, even when terminal olefins are present. On the other hand, molybdenum appears to work relatively well, as shown in Eqs. 30 [207] and 31 [208]. Under some conditions polymerization (ADMET) to give poly-thioethers is a possible alternative [26]. Aryloxide tungsten catalysts have also been employed successfully to prepare thioether derivatives [107,166,169]. Apparently the mismatch between a hard earlier metal center and a soft sulfur donor is what allows thioethers to be tolerated by molybdenum and tungsten. Similar arguments could be used to explain why cyclometalated aryloxycarbene complexes of tungsten have been successfully employed to prepare a variety of cyclic olefins such as the phosphine shown in Eq. 32 [107,193]. 

Dimethyl sulfoxide has found application as a solvent for electrochemical studies of Mo(VI) and Mo(V) complexes of quinol derivatives (287). Sulfoxides have also been examined as extractants for the separation of molybdenum and tungsten from acid solutions (218). 

Chromium(IV) and chromium(V), previously encountered as the oxides and halides and as unstable intermediates in solution, are now represented by complexes of ligands stabilized by heavy substitution against oxidation by the metal ion, and oxo and nitrido derivatives. These remain unimportant oxidation states compared with molybdenum and tungsten. 

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