论文部分内容阅读
本文利用原位红外光谱方法研究了三钌乙烯酮化合物在无机载体SiO_2、SiO_2-Al_2O_3和MgO表面上的负载,发现[Ru_3(CO)_9(CCO)]~(2-)分别同SiO_2和SiO_2-Al_2O_3表面上的羟基反应,选择性地定量形成[HRu_3(CO)_9(CCO)]~-/SiO_2和H_2Ru_3(CO)_9(CCO)/SiO_2-Ai_2O_3,而在MgO表面上,[Ru_3(CO)_9(CCO)]~(2-)保持其结构。对~(13)CO同位素交换,H_2Ru_3(CO)_9(CCO)/SiO_2-Al_2O_3显示了很高活性,而[Ru_3(CO)_9(CCO)]~(2-)/MgO则完全不反应。在甲基化反应中,[Ru_3(CO)_9(CCO)]~(2-)/MgO对CH_3I显示了很高活性,但对CH_3Li却不反应,对H_2Ru_3(CO)_9(CCO)/SiO_2-Al_2O_3,它与CH_3I不显示活性,但却和CH_3Li较易反应;[HRu_3(CO)_9(CCO)]~-/SiO_2的甲基化的活性顺序处于上述MgO和SiO_2-Al_2O_3担体上的簇合物之间。通过乙烯甲酰化反应可以看到,在(Ru_3(CO)_9(CCO)]~(2-)/MgO上,对于含氧化合物的形成显示了高活性,而对于H_2Ru_3(CO)_9(CCO)/SiO_2-Al_2O_3则有利于形成烃类化合物。
In this paper, the in-situ IR spectra of three ruthenium ketene compounds loaded on the surface of inorganic supports SiO 2, SiO 2 -Al 2 O 3 and MgO were studied. It was found that [Ru_3 (CO) _9 (CCO) The reaction of hydroxyl groups on the surface of Al 2 O 3 with selective oxidation of [HRu_3 (CO) _9 (CCO)] ~ - / SiO_2 and H_2Ru_3 (CO) _9 (CCO) / SiO_2-Ai_2O_3, CO) _9 (CCO)] ~ (2-) maintains its structure. The activity of H_2Ru_3 (CO) _9 (CCO) / SiO_2-Al_2O_3 was very high for ~ (13) CO isotope exchange, whereas [Ru_3 (CO) _9 (CCO)] ~ (2 -) / MgO did not react at all. In the methylation reaction, [Ru_3 (CO) _9 (CCO)] ~ (2 -) / MgO showed high activity for CH_3I, but not for CH_3Li. -Al_2O_3, which showed no activity with CH_3I but was more reactive with CH_3Li. The order of methylation of [HRu_3 (CO) _9 (CCO)] ~ - / SiO_2 was in the order of clusters on the MgO and SiO_2-Al_2O_3 supports Between compounds. It was found that the formation of oxygenated compounds was highly active on (Ru_3 (CO) _9 (CCO)] ~ (2 -) / MgO through the reaction of vinyl formalization, while that of H_2Ru_3 (CO) _9 ) / SiO 2 -Al 2 O 3 is conducive to the formation of hydrocarbon compounds.