THE ACTIVATION OF INERT CARBON-OXYGEN AND CARBON-HYDROGEN BONDS BY REACTION WITH METAL ATOMS

[摘要] The activation of the carbon-oxygen bonds in ethers and the carbon-hydrogen bonds in alkanes is accomplished by reaction at cryogenic temperatures with metal atoms. Calcium, strontium, and barium react with dimethyl ether to produce yellow-orange pyrophoric solids. Hydrolysis of these solids yields hydrocarbon products and the metal hydroxide. The cocondensation reactions of transition metals with dimethyl ether are also investigated. Chromium, manganese, iron, cobalt, and nickel react to give hydrocarbons upon hydrolysis but copper and zinc fail to react. The photolytic insertions of metal atoms into the carbon-hydrogen bonds of methane are studied using infrared matrix isolation spectoscopy. The initial product is a methyl-metal hydride. The reaction takes place for the metals: manganese, iron, cobalt, copper, silver, gold, and zinc. No reaction was observed for calcium, titanium, chromium, or nickel.

[发布机构] Rice University