Berthelot Mathieu, Akhssas Fatima, Dimé Abdou K D, Bousfiha Asmae, Echaubard Julie, Souissi Ghada, Cattey Hélène, Lucas Dominique, Fleurat-Lessard Paul, Devillers Charles H
UMR6302, CNRS, Univ. Bourgogne Franche-Comté, Institut de Chimie Moléculaire de l'Université de Bourgogne, 9 avenue Alain Savary, 21000 Dijon, France.
Département de Chimie, UFR SATIC, Université Alioune Diop de Bambey, MGWC+9M6 Bambey, Senegal.
Inorg Chem. 2022 May 16;61(19):7387-7405. doi: 10.1021/acs.inorgchem.2c00435. Epub 2022 May 2.
The synthesis and characterization of zinc(II) -pyridin-2-ylthio-porphyrins are presented in this manuscript. The (electro)chemical oxidation of [5-(pyridin-2-ylthio)-10,20-bis(-tolyl)-15-phenylporphyrinato] zinc(II) or [5,15-bis(pyridin-2-ylthio)-10,20-bis(-tolyl)porphyrinato] zinc(II) leads to the formation of one or two C-N bond(s) by intramolecular nucleophilic attack of the peripheral thiopyridinyl fragment(s) on the neighboring β-pyrrolic position(s) (C-N fusion reaction). In addition, the chemical oxidation of [5-(pyridin-2-ylthio)-10,20-bis(-tolyl)porphyrinato] zinc(II), , bearing one free position, mainly affords the ,-dimer. Further stepwise electrochemical oxidation selectively produces the mono and bis C-N fused ,-dimer. The resulting pyridinium derivatives exhibit important changes in their physicochemical properties (NMR, UV-vis, CV) as compared to their initial unfused precursors. Also, the X-ray crystallographic structures of three unfused monomers, one unfused ,-dimer, and two C-N fused monomers are presented.
本文介绍了锌（II）-吡啶-2-硫基卟啉的合成与表征。[5-（吡啶-2-硫基）-10,20-双（对甲苯基）-15-苯基卟啉锌（II）]或[5,15-双（吡啶-2-硫基）-10,20-双（对甲苯基）卟啉锌（II）]的（电）化学氧化通过外围硫代吡啶基片段对相邻β-吡咯位置的分子内亲核攻击导致形成一个或两个C-N键（C-N融合反应）。此外，具有一个自由位置的[5-（吡啶-2-硫基）-10,20-双（对甲苯基）卟啉锌（II）]的化学氧化主要生成α，α-二聚体。进一步的逐步电化学氧化选择性地产生单和双C-N融合的α，α-二聚体。与它们最初未融合的前体相比，所得的吡啶鎓衍生物在其物理化学性质（NMR、UV-vis、CV）方面表现出重要变化。此外，还给出了三种未融合单体、一种未融合的α，α-二聚体和两种C-N融合单体的X射线晶体结构。
