Institute of Inorganic Chemistry, Johannes Kepler University Linz (JKU), Altenberger Strasse 69, A-4040 Linz, Austria.
Inorg Chem. 2011 Jul 18;50(14):6788-97. doi: 10.1021/ic200840m. Epub 2011 Jun 13.
An efficient metalation procedure for bismuth complexes with meso-substituted corrole ligands is presented. Reaction of 5,10,15-tris-pentafluorophenylcorrole H(3)(TpFPC) with Bi{N(SiMe(3))(3)} converts the free ligand H(3)(TpFPC) to a neutral low-valent species Bi(TpFPC), which has been characterized by different spectroscopic techniques. (Spectro)electrochemical studies were performed in order to describe the redox potentials of the Bi(TpFPC) complex and to ascribe the sites of electron transfer. The first crystal structure of a bismuth corrole is presented and compared to the geometry-optimized molecular structure obtained with density functional theory (DFT) calculations. We show an example of a 4-coordinate metallocorrole with a very large out-of-plane displacement and significant doming. The electronic structure of the novel bismuth corrole system is discussed in detail. Time-dependent DFT results support the proposed assignment of electronic transitions observed for the Bi(TpFPC) derivative. To account for the reactivity we investigated the photocatalytic properties of the Bi(TpFPC) complex.
本文介绍了一种高效的含介孔取代卟啉配体的铋配合物的金属化方法。5,10,15-三-(五氟苯基)卟啉 H(3)(TpFPC)与 Bi{N(SiMe(3))(3)}反应，将游离配体 H(3)(TpFPC)转化为中性低价物种 Bi(TpFPC)，并用不同的光谱技术对其进行了表征。为了描述 Bi(TpFPC)配合物的氧化还原电位并确定电子转移的位置，进行了（光谱）电化学研究。本文还首次呈现了一个铋卟啉的晶体结构，并与通过密度泛函理论（DFT）计算得到的优化分子结构进行了比较。我们展示了一个具有非常大的面外位移和显著的凸起的 4 配位金属卟啉的例子。详细讨论了新型铋卟啉体系的电子结构。含时密度泛函理论（TD-DFT）的结果支持了对观察到的 Bi(TpFPC)衍生物的电子跃迁的提议。为了研究反应性，我们研究了 Bi(TpFPC)配合物的光催化性质。
