Mono- and Diboron Corroles: Factors Controlling Stoichiometry and Hydrolytic Reactivity
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- 作者：Amelia M. Albrett ; Kolle E. Thomas ; Stefanie Maslek ; Anna M艂odzianowska ; Jeanet Conradie ; Christine M. Beavers ; Abhik Ghosh ; Penelope J. Brothers
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：June 2, 2014
- 年：2014
- 卷：53
- 期：11
- 页码：5486-5493
- 全文大小：404K
- 年卷期：v.53,no.11(June 2, 2014)
- ISSN：1520-510X
文摘
The first example of a diboryl corrole complex, [(BF2)2(Br8T(4-F鈥揚)C)]鈭?/sup> (Br8T(4-F鈥揚)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)]鈭?/sup> 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鈥揚)C), 5,10,15-tris(4-trifluoromethylphenyl)corrole (T(4-CF3鈥揚)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路路路HN hydrogen bonding may be significant in stabilizing these complexes. Further examples of the anionic diboron corrole [B2OF2(Cor)]鈭?/sup> 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.