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本文采用CNDO/2(M)程序研究了三铁核羰基原子簇络合物HFe_3(CO)_(11)~-的电子结构,及其在丙烯羰基化过程中可能的催化作用。结果说明HFe3(CO)_(11)~-的桥键结构是稳定的,它具有催化活性,并且活性部位在桥键一湍,证实了内烯从桥端向催化剂进攻从能量上是有利的。通过计算说明HFe_3(CO)_(11)~-催化丙烯羰基化生成正丁醇的活化能高于生成异丁醇的活化能。上述结果均与郑作光等的实验结论一致。同时本文选择了一组适当的铁原子的参数,在改善计算收敛性等方面对原CNDO/2程序作了一定的改进。
In this paper, the CNDO / 2 (M) procedure has been used to study the electronic structure of the ferric carbonyl cluster complex HFe_3 (CO) _ (11) ~ - and its possible catalytic activity in the carbonylation of propylene. The results indicate that the bridging structure of HFe3 (CO) _ (11) ~ - is stable, it has catalytic activity, and the active site is under bridged bond, demonstrating that it is energetically advantageous for the internal olefin to attack from the bridgehead to the catalyst . The results show that the activation energy of n-butanol is higher than that of isobutanol when HFe_3 (CO) _ (11) ~ - catalyzed carbonylation of propylene. The above results are consistent with the experimental conclusion of Zheng Zuoguang et al. At the same time, we choose a set of appropriate parameters of iron atom, and make some improvements to the original CNDO / 2 program in terms of improving the computational convergence.