Tungsten hexacarbonyl complexes synthesis

The binary tungsten-carbon system (Fig. 4.1) [4.13-4.15] is of high technical importance. It contains three intermediate compounds W2C(P), WCi ((y), and WC(5), the latter being the main constituent in most of the commercial cemented carbides (hardmetals see Chapter 9). Besides, ternary and even more complex compoimds exist which are of interest in alloyed steels and cemented carbides. Tungsten hexacarbonyl is an important precursor for organic synthesis. 

Electrocycylic ring closure combined with Diels-Alder addition has been employed to derive all four rings of the tetracyclic ring system in the steroids by means of a one pot synthesis (ref.198). Thus, from the triflate of hex-4-ynol and the readily available hexa-1,5-diyne a triyne intermediate was obtained which with chromium or tungsten hexacarbonyl formed a triyne carbene complex. This with a 1,3-dialkoxybuta-1,3-diene in acetonitrile with carbon monoxide 0 atmosphere) initially at ambient temperature and then at 110°C over 24 hours afforded a 62% yield of the two products shown [(1) R = TBS (2) R = H, (1) (2) 5 2]. 

In 1964, Fischer prepared and characterized unambiguously the first metal carbene complex 3 obtained by nucleophilic attack of phenyl lithium at tungsten hexacarbonyl followed by 0-alkylation. This was followed by Schrock s synthesis of a high oxidation state metal alkylidene complex 4 obtained by a-hydrogen abstraction from tris(neopentyl) tantalumfv) dichloride (Scheme 1.1)/ ... 

A number of attempts have been made over the years to develop reproducible synthetic routes to six- and seven-coordinate isocyanide complexes of molybdenum and tungsten. Two of the older methods, namely, the reaction of the hexacarbonyls with halogens in the presence of an isocyanide (775,116) or reactions of the salt Ag4Mo(CN)8 with isocyanides (74), have given six- and seven-coordinate products. Recently, however, the discovery of the reductive or nonreductive cleavage of multiple metal - metal bonds in dinuclear group VIA compounds by isocyanides has provided a facile route to the synthesis of a variety of homoleptic and related isocyanide complexes of these metals in reasonable yields. 

The photochemical synthesis of the tungsten carbonyl metallocarborane [Eq. (18) ] is also effective in the preparation of the molybdenum carbonyl analog. The resulting air-sensitive complexes show chemical behavior similar to the cyclopentadienyl analogs, C5H5M(CO)3, in that they undergo protonation with anhydrous HOI and met.hylation with CH3I. They also react further with metal hexacarbonyls to afford bimetallic complexes 54) ... 

---