Division of Quantum Chemistry and Physical Chemistry, Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium.
Phys Chem Chem Phys. 2020 Nov 7;22(41):23908-23919. doi: 10.1039/d0cp04401f. Epub 2020 Oct 19.
We use a variety of computational methods to characterize and compare the hydrogen atom transfer (HAT) and epoxidation reaction pathways for oxidation of cyclohexene by an iron(iv)-oxo complex. Previous B3LYP calculations have led to predictions that both alcohol (from the HAT route) and epoxide should be formed in similar amounts, which was not in agreement with experiment where only the HAT product was observed. We show here that ab initio calculations which can take both static and dynamic correlation into account are needed to explain the experimentally observed dominance of the HAT process. Since these systems do not have very strong multireference character we have also tested different flavours of local coupled cluster methods. We suggest that further improvements are necessary before they can provide highly accurate results for these systems.
我们使用各种计算方法来描述和比较铁（iv）-氧配合物氧化环己烯的氢原子转移（HAT）和环氧化反应途径。先前的 B3LYP 计算导致了这样的预测，即醇（来自 HAT 途径）和环氧化物都应以相似的量形成，这与仅观察到 HAT 产物的实验结果不一致。我们在这里表明，需要考虑静态和动态相关的从头算计算才能解释实验观察到的 HAT 过程的优势。由于这些系统没有很强的多参考特征，我们还测试了不同风味的局部耦合簇方法。我们认为，在这些系统中提供高度准确的结果之前，还需要进一步改进。
