Albrett Amelia M, Thomas Kolle E, Maslek Stefanie, Młodzianowska Anna, Conradie Jeanet, Beavers Christine M, Ghosh Abhik, Brothers Penelope J
School of Chemical Sciences, The University of Auckland , Private Bag 92019, Auckland, New Zealand.
Inorg Chem. 2014 Jun 2;53(11):5486-93. doi: 10.1021/ic500114k. Epub 2014 Mar 31.
The first example of a diboryl corrole complex, (BF2)2(Br8T(4-F-P)C) (Br8T(4-F-P)C = trianion of 2,3,7,8,12,13,17,18-octabromo-5,10,15-tris(4-fluorophenyl)corrole), has been isolated using the strongly electron-withdrawing and sterically crowded triaryl octabromocorrole ligand. Density functional theory (DFT) calculations show that the hydrolysis reaction producing the partially hydrolyzed complexes B2OF2(Cor) is more favored for the less sterically crowded triaryl corrole complexes. Monoboryl complexes BF2(H2Cor) (Cor = trianions of 5,10,15-triphenylcorrole (TPC), 5,10,15-tris(4-methylphenyl)corrole (T(4-CH3-P)C), 5,10,15-tris(4-trifluoromethylphenyl)corrole (T(4-CF3-P)C), and 5,10,15-tris(pentafluorophenyl)corrole (TPFPC)) were prepared and characterized. The experimental data are consistent with an out-of-plane dipyrrin coordination mode for these complexes, and DFT optimizations suggest that internal BF···HN hydrogen bonding may be significant in stabilizing these complexes. Further examples of the anionic diboron corrole B2OF2(Cor) containing the electron-withdrawing 5,10,15-tris(pentafluorophenyl)corrole (TPFPC) and the sterically hindered 10-(4-methoxyphenyl)-5,15-dimesitylcorrole (Mes2(4-MeOP)C) trianions are reported.
二硼基卟啉配合物[(BF₂)₂(Br₈T(4 - F - P)C)]⁻（Br₈T(4 - F - P)C = 2,3,7,8,12,13,17,18 - 八溴 - 5,10,15 - 三(4 - 氟苯基)卟啉的三阴离子）的首个实例，是利用强吸电子且空间位阻大的三芳基八溴卟啉配体分离得到的。密度泛函理论（DFT）计算表明，对于空间位阻较小的三芳基卟啉配合物，生成部分水解的配合物[B₂OF₂(Cor)]⁻的水解反应更有利。制备并表征了单硼基配合物BF₂(H₂Cor)（Cor = 5,10,15 - 三苯基卟啉（TPC）、5,10,15 - 三(4 - 甲基苯基)卟啉（T(4 - CH₃ - P)C）、5,10,15 - 三(4 - 三氟甲基苯基)卟啉（T(4 - CF₃ - P)C）和5,10,15 - 三(五氟苯基)卟啉（TPFPC）的三阴离子）。实验数据与这些配合物的面外二吡咯配位模式一致，DFT优化表明，分子内BF···HN氢键在稳定这些配合物方面可能起重要作用。还报道了含吸电子的5,10,15 - 三(五氟苯基)卟啉（TPFPC）和空间位阻大的10 - (4 - 甲氧基苯基)-5,15 - 二甲基苯基卟啉（Mes₂(4 - MeOP)C）三阴离子的阴离子二硼卟啉[B₂OF₂(Cor)]⁻的更多实例。
