Yagi Atsumi, Shinokubo Hiroshi
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan.
Chemistry. 2020 Jul 2;26(37):8210-8213. doi: 10.1002/chem.202002053. Epub 2020 May 29.
The neighboring effect of two adjacent heteroatoms influences the structures and properties of heterocyclic compounds. Herein, we demonstrated that the introduction of two adjacent sp nitrogen atoms into a porphyrinic skeleton significantly enhanced its Brønsted basicity due to the repulsive interaction between two lone pairs on the nitrogen atoms. Palladium- and copper-templated ring closure of dichlorobis(dipyrrin) with hydrazine hydrate provided meso-diazacorrphycene palladium and copper complexes in good yields. The structural, magnetic, and electrochemical properties of the diazacorrphycene complexes were investigated experimentally and theoretically to elucidate the effect of the meso-nitrogen atoms.
两个相邻杂原子的邻位效应会影响杂环化合物的结构和性质。在此，我们证明，由于氮原子上两个孤对电子之间的排斥相互作用，将两个相邻的sp氮原子引入卟啉骨架会显著增强其布朗斯特碱性。二氯双（二吡咯）与水合肼在钯和铜模板作用下的闭环反应以良好的产率提供了中位二氮杂卟吩钯和铜配合物。通过实验和理论研究了二氮杂卟吩配合物的结构、磁性和电化学性质，以阐明中位氮原子的作用。
