Institut für Anorganische und Angewandte Chemie, Department Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany.
J Phys Chem A. 2011 Dec 1;115(47):13885-95. doi: 10.1021/jp2061283. Epub 2011 Nov 2.
Coordinative polymerization of fluorinated olefins is still a challenging task. We analyzed the catalytic properties of diimido chromium VI compounds computationally by density functional methods. It was found that reactivity predictions depend strongly on the density functional chosen for the computations. Therefore, DFT calculations were calibrated to high level wave function theory calculations. Then geometrical parameters, which can be tuned by a ligand, were scanned to elucidate their influence on the catalytic activity. Having arrived at an optimal parameter set, we randomly assembled chromium complexes from a fragments database and automatically checked for their activities. This led to the proposal of three exemplary catalyst candidates.
含氟烯烃的配位聚合仍然是一项具有挑战性的任务。我们通过密度泛函方法计算分析了二亚胺六价铬化合物的催化性能。结果表明，反应性预测强烈依赖于所选的密度泛函方法。因此，我们对 DFT 计算进行了校准，以使其与高精度波函数理论计算相匹配。然后，我们扫描了可以通过配体进行调节的几何参数，以阐明它们对催化活性的影响。在获得最佳参数集后，我们从碎片数据库中随机组装铬配合物，并自动检查它们的活性。这提出了三个典型的催化剂候选物。
