| The cocondensation reactions of molybdenum trioxide vapor with methanol, ethanol, isopropanol, n-butanol, water, tetrahydrofuran, 2,2',4,4'-tetramethyltetrahydrofuran, furan, diethylether, acetone, carbon disulfide, methanethiol, thiophene, 2,2'-dimethylthiophene, phenylacetylene, t-butylacetylene, cyclopentene, cyclohexene, cycloctene, cis-2-pentene, t-butylethylene, hexene, cyclopentadiene, cyclohexane, propene, benzene, and toluene at -196(DEGREES)C were investigated. The cocondensation products of molybdenum trioxide with methanol, water, carbon disulfide, tetrahydrofuran, phenylacetylene, cyclopentene and cyclohexene were chosen for further characterization. The methanol cocondensate was shown to be Mo(,2)O(,5)(OCH(,3))(,2).2CH(,3)OH, residual unreacted MoO(,3) and physisorbed methanol. Photolysis of a slurry of the methanol cocondensate in methanol under dioxygen selectively gave dimethoxymethane. The conversion was shown to be catalytic with 55 turnovers over an 18 day period. The water cocondensate was shown to be a new molybdenum trioxide dihydrate, different from known yellow monoclinic MoO(,3).2H(,2)O. The carbon disulfide cocondensate was an amorphous solid with a bulk composition of 0.13 mole carbon disulfide per mole MoO(,3). The presence of carbon dioxide and carbonyl sulfide in the reaction vessel after cocondensation of MoO(,3) with CS(,2) and warming to room temperature indicated sulfur-oxygen exchange occurred on the molybdenum. Carbon dioxide appears to be formed at anion vacancies, while carbonyl sulfide appears to be formed on fully oxidized molybdenum trioxide. The THF cocondensate was an amorphous solid with a bulk composition of 0.57 mole THF per mole MoO(,3). A solution of the THF cocondensate in wet THF containing 18-crown-6 exposed to air gave crystals of the seven coordinate peroxomolybdenum complex, MoO(O(,2))(,2)(H(,2)O)(,2) .18-crown-6.H(,2)O, after 35 days. Additional studies showed the peroxomolybdenum was formed from reaction of molybdenum oxide with H(,2)O(,2) formed in situ from (alpha)-hydroperoxotetrahydrofuran. Chloroform extraction of a sodium hydroxide slurry of the phenylacetylene cocondensate yielded trans-polyphenylacetylene. A saturated polymer was recovered upon chloroform extraction of a sodium hydroxide slurry of both the cyclopentene cocondensate and the cyclohexene cocondensate. |
