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Updated: Jun 5, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Sub-m-benziporphyrin: a subcarbaporphyrinoid and its BIII complex with an unprecedented planar tridentate
Le Liu1, Shuangji Song1, Jiyeon Lee2
1Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Educational of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University Changsha 410081 China jxsong@hunnu.edu.cn atsuhiroosuka@hunnu.edu.cn.
Abstract:
Sub-m-benziporphyrins were synthesized by Pd-catalyzed cross-coupling of α,α'-diboryl-m-benzitripyrrane with 9,10-bis(1,1-dibromomethylenyl)anthracene. Reaction of sub-m-benziporphyrin with PhBCl2 and triethylamine gave its B-phenyl complex as a tetracoordinate nonaromatic BIII complex. In contrast, the reaction with BBr3 and triethylamine furnished a neutral BIII porphyrinoid with a planar and triangular coordination as the first example, in which the m-phenylene unit was partially reduced, allowing for the global 14π-aromatic circuit. This aromatic BIII complex is stable and inert towards nucleophiles such as pyridine, 4-dimethylaminopyridine, and fluoride anions but undergoes an oxygen-insertion reaction upon refluxing in the air. In addition, this BIII complex displays structured vibronic Q-bands, slow S1-state decay, and fluorescence (Φ F = 0.30 and τ F = 9.7 ns), in line with its aromatic nature, while the nonaromatic BIII complexes show ill-defined absorption spectra and very fast S1-state decays.
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