GB892142A - Preparing metal carbonyls - Google Patents

Abstract

Carbonyls of metals of Group Vb and VIb, e.g. vanadium, chromium, molybdenum and tungsten, are prepared by reacting a salt, oxide, sulphide, alcoholate or phenate of the metal in question with carbon monoxide and a stable organo compound of a group IIb or IIIa element, e.g. Zn, Cd, Hg, B, Al, Ga, In or Tl. Organo compounds specified include dimethylzinc, di-isopropyl-zinc, dioctylzinc, methylethylzinc, n-heptyl-n-octylzinc, n-butylzinc bromide, ethylzinc hydride, dicyclohexylzinc, sodium zinc triethyl, diphenylzinc, diethylcadmium, diethylmercury, dibenzylmercury, triethylboron, ethylborondifluoride, sodium tetraethylborate, methyldiethylaluminium, tri-isooctyl-aluminium, methylethyloctylaluminium, diethylaluminium hydride, octylaluminium dihydride, lithium aluminium tetraethyl, potassium aluminium dioctyl dihydride, dimethylaluminium chloride, ethylaluminium sesquichloride, tripropylgallium, trimethylindium, triphenylaluminium, sodium aluminium diethyl acetylide, and triethylthallium. In Example I, a mixture of chromium trioxide, diethylzinc, and diethyl ether in an inert atmosphere of nitrogen is pressurized with 2,500 p.s.i.g. of CO and heated to 100 DEG C. with continuous agitation for four hours. After cooling to 30 DEG C., the mixture is quenched with dilute HCl, and chromium hexacarbonyl is recovered. In Examples II and III, molybdenum hexacarbonyl is obtained using diethylzinc, tetrahydrofuran, and molybdenum trichloride or trioxide, in Example IV tungsten hexacarbonyl is similarly obtained, in Example V vanadium petacarbonyl dimer is similarly obtained using diphenylzinc, and in Example VI chromium hexacarbonyl is obtained from chromons acetylacetate. In Example VII, vanadium pentacarbonyl is obtained using vanadium dichloride, diethylaluminium hydride and diethyl ether. In Examples IX and X, chromium hexacarbonyl is prepared using triethylaluminium and either chromons acetylacetate and tetrahydrofuran or chromic chloride and diethyl ether. In Example XI, molybdenum hexacarbonyl is obtained from molybdenum dichloride, triethylaluminium and diethyl ether. Examples XII and XIII are similar, producing tungsten and molybdenum hexacarbonyls from tungsten and molybdenum trioxides. Numerous other organic diluents, which are hydrocarbons, ethers, amines, pyridines, and isoquinoline.