Synthesis, structures, and aromaticity of phosphole-containing porphyrins and their metal complexes

Our recent studies on the synthesis, structures, and aromaticity of phosphole-containing porphyrins and their metal complexes are summarized. Core-modified P, X, N2-porphyrins (X = S, N) are accessible from a σ4-phosphatripyrrane and the corresponding 2, 5-difunctionalized heteroles in a few steps. X-ray structural analysis of the σ3-P, N3 porphyrin revealed that it possesses a slightly distorted 18π plane. The phosphorus atom incorporated at the core plays an important role in producing unprecedented reactivity and coordinating ability for the porphyrin ring. The P, N3 free base reacts with [RhCl(CO)2]2 in dichloromethane, ultimately yielding an 18π P, N3–rhodium(III) complex, whereas the P, S, N2 free base undergoes redox-coupled complexation with zero valent group 10 metals to afford the corresponding P, S, N2-isophlorin–metal(II) complexes. The aromaticity of the free-base porphyrins and the metal complexes was uncovered based on both experimental and theoretical results. It is of particular interest that the P, S, N2-isophlorin –metal complexes exhibit only a weak antiaromaticity in terms of the magnetic criterion

ホスホールを含む大環状化合物の基礎物性、配位能、および反応性に関する研究

京都大学0048新制・課程博士博士(工学)甲第15582号工博第3294号新制||工||1497(附属図書館)28103京都大学大学院工学研究科分子工学専攻(主査)教授 今堀 博, 教授 田中 一義, 教授 辻 康之学位規則第4条第1項該当Doctor of Philosophy (Engineering)Kyoto UniversityDFA