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本文报导用加温加压原位红外光谱法在1:1的CO+H_2气氛中跟踪铁—钴异核金属簇催化剂[K_4N][FeCo_3(CO)_(12)](R=乙基、丁基、十六烷基、苄基三甲基、苄基三乙基等)在三种不同极性的溶剂(甲醇、甲苯、正庚烷)中的热分解反应。实验证明,在烯烃醛化条件下(120—150℃,4.0MPa),这些金属簇合物均分解生成Fe(CO)_5、Co_2(CO)_3、HCo(CO)_4和Co(CO)_4~-的盐。HCo(CO)_4和Co(CO)_4~-均为醛化活性物种。在甲苯中升温不超过150℃,并增加CO分压,再降至室温时,发现簇的吸收复出。R_4N~+的存在对催化剂体系有稳定作用。
In this paper, we report the IR spectra of iron-cobalt heteronuclear metal clusters [K_4N] [FeCo_3 (CO) _ (12)] (R = ethyl, Butyl, cetyl, benzyltrimethyl, benzyltriethyl etc.) in three different polar solvents (methanol, toluene, n-heptane). Experiments show that these metal clusters decompose to form Fe (CO) _5, Co_2 (CO) _3, HCo (CO) _4 and Co (CO) _4 under the conditions of olefinic aldehyde (120-150 ℃, ~ - salt. Both HCo (CO) _4 and Co (CO) _4 ~ - are aldehyde active species. Heating in toluene does not exceed 150 ℃, and increase the partial pressure of CO, and then down to room temperature, the absorption of the cluster was found to come back. The presence of R_4N ~ + has a stabilizing effect on the catalyst system.