Kazan National Research Technological University, K. Marx Street 68, 420015 Kazan, Russia.
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.
Int J Mol Sci. 2020 Nov 29;21(23):9085. doi: 10.3390/ijms21239085.
Based on the results of a quantum chemical calculation using the DFT method with the OPBE/TZVP and B3PW91/TZVP levels, the possibility of the existence of three cobalt heteroligand complexes containing in the inner coordination sphere porphyrazine, di[benzo]- and tetra[benzo]porphyrazine, and two oxygen (O) ions with probable oxidation state VI of Co, which is unknown for this element at the present time, was shown. Data on the structural parameters are presented. It was shown that CoN chelate nodes as well as all metal-chelate and non-chelate cycles in each of these complexes, were strictly planar. Besides, the bond angles formed by two donor nitrogen atoms and a Co atom were close or equal to 90°, while the bond angles formed by donor atoms N, Co, and O, in most cases, albeit insignificantly, differed from this value. Good agreement between the calculated data obtained using the above two versions of the DFT method was found. Standard thermodynamic parameters of formation (standard enthalpy Δ, entropy and Gibbs's energy Δ) for the indicated complexes were presented too.
基于使用 DFT 方法（OPBE/TZVP 和 B3PW91/TZVP 能级）进行量子化学计算的结果，表明存在三种钴杂配位配合物的可能性，这些配合物在其内部配位球中含有卟嗪、二[苯并]-和四[苯并]卟嗪，以及两个氧（O）离子，它们可能具有当前未知的 Co 的六价氧化态，同时还给出了结构参数的数据。结果表明，在这些配合物中的每个配合物中，CoN 螯合节点以及所有金属螯合和非螯合环都是严格平面的。此外，由两个供体氮原子和一个 Co 原子形成的键角接近于或等于 90°，而由供体原子 N、Co 和 O 形成的键角，在大多数情况下，虽然不明显，但与该值不同。发现使用上述两种 DFT 方法计算得到的数据之间具有良好的一致性。还给出了所指配合物的形成（标准焓 Δ，熵 和吉布斯自由能 Δ）的标准热力学参数。
