Research Laboratories, Eastman Chemical Company, Kingsport, Tennessee 37662, USA.
Inorg Chem. 2010 May 17;49(10):4606-10. doi: 10.1021/ic100182n.
The thermal decomposition of [py(3)Co(3)O(OAc)(5)OH][PF(6)] in acetic acid solution in the absence of oxygen produced carbon dioxide, methane, carbon monoxide, picoline, and formic acid as the major products. The ratio of the products was affected by the water concentration and acidity of the mixture. Increased water concentration caused a decrease in methane and an increase in carbon monoxide. Decreased acidity resulted in an increase in methane and a decrease in carbon monoxide. Isotopic labeling experiments showed that some of the carbon monoxide originated as the carboxyl group of the acetic acid. Labeling experiments also showed that formaldehyde and formic acid could be converted to carbon monoxide under the reaction conditions. Two pathways leading to the formation of carbon monoxide were proposed; one involving the decomposition of glyoxylic acid and another involving the oxidation of the methyl radical by cobalt(III).
在无氧条件下，[py(3)Co(3)O(OAc)(5)OH][PF(6)]在醋酸溶液中的热分解产生了二氧化碳、甲烷、一氧化碳、吡啶和甲酸等主要产物。产物的比例受混合物中水浓度和酸度的影响。增加水浓度会导致甲烷减少而一氧化碳增加。降低酸度会导致甲烷增加而一氧化碳减少。同位素标记实验表明，部分一氧化碳来自于醋酸的羧基。标记实验还表明，在反应条件下，甲醛和甲酸可以转化为一氧化碳。提出了两种生成一氧化碳的途径；一种涉及乙醛酸的分解，另一种涉及钴(III)氧化甲基自由基。
