Kazan Department of Joint Supercomputer Center of Russian Academy of Sciences-Branch of Federal Scientific Center "Scientific Research Institute for System Analysis of the RAS", Lobachevskii Street 2/31, 420111 Kazan, Russia.
Department of Analytical Chemistry, Certification and Quality Management, Kazan National Research Technological University, K. Marx Street 68, 420015 Kazan, Russia.
Int J Mol Sci. 2023 Mar 29;24(7):6442. doi: 10.3390/ijms24076442.
By using quantum chemical calculation data obtained by the DFT method with the B3PW91/TZVP and OPBE/TZVP levels, the possibility of the existence of three Fe(V) complexes, each of which contains in the inner coordination sphere porphyrazine/-di[benzo]porphyrazine/tetra[benzo]porphyrazine (phthalocyanine), oxygen (O) and fluorine (F) ions, was shown. Key geometric parameters of the molecular structure of these heteroligand complexes are given; it is noted that FeN4 chelate nodes, and all metal-chelate and non-chelate cycles in each of these compounds, are practically planar with the deviation from coplanarity, as a rule, by no more than 0.5°. Furthermore, the bond angles between two nitrogen atoms and an Fe atom are equal to 90°, or less than this by no more than 0.1°, while the bond angles between donor atoms N, Fe, and O or F, in most cases, albeit insignificantly, differ from this value. Nevertheless, the bond angles formed by Fe, O and F atoms are exactly 180°. It is shown that good agreement occurs between the structural data obtained using the above two versions of the DFT method. NBO analysis data for these complexes are presented; it is noted that, according to both DFT methods used, the ground state of the each of three complexes under consideration may be a spin quartet or spin doublet. Additionally, standard thermodynamic parameters of formation (standard enthalpy ∆, entropy and Gibbs's energy ∆) for the macrocyclic compounds under consideration are calculated.
使用 DFT 方法中的 B3PW91/TZVP 和 OPBE/TZVP 能级获得的量子化学计算数据，表明存在三种 Fe(V) 配合物的可能性，其中每个配合物都在内部配位球中包含卟啉/-二[苯]卟啉/四[苯]卟啉（酞菁）、氧（O）和氟（F）离子。给出了这些杂配位配合物分子结构的关键几何参数；值得注意的是，FeN4 螯合节点以及这些化合物中的所有金属-螯合和非螯合环实际上都是平面的，与共面性的偏差通常不超过 0.5°。此外，两个氮原子和一个 Fe 原子之间的键角等于 90°，或者不超过 0.1°，而供体原子 N、Fe 和 O 或 F 之间的键角在大多数情况下，虽然微不足道，但与该值略有不同。然而，Fe、O 和 F 原子之间形成的键角恰好为 180°。结果表明，使用上述两种 DFT 方法获得的结构数据之间存在良好的一致性。给出了这些配合物的 NBO 分析数据；值得注意的是，根据使用的两种 DFT 方法，所考虑的三种配合物中的每一种的基态可能是自旋四重态或自旋双态。此外，还计算了所考虑的大环化合物的标准生成焓 ∆、熵 和吉布斯自由能 ∆标准热力学参数。
