Electrosynthesis and X‐ray Crystallographic Structure of Zn^IImeso‐Triaryltriphenylphosphonium Porphyrin and Structural Comparison with Mg^IImeso‐Triphenylphosphonium Porphine

Abstract

The electrochemical oxidation of ZnII 5,15‐bis(p‐tolyl)‐10‐phenylporphyrin (1‐Zn) in the presence of triphenylphosphine (PPh3) leads to the meso‐substituted triphenylphosphonium porphyrin, coordinated by one P(O)Ph3 molecule [1‐Zn‐PPh3+,PF6–·P(O)Ph3] in good yield (84 %). This cationic porphyrin was characterized by NMR, MALDI‐TOF mass spectrometry, UV/Vis. absorption spectroscopy and X‐ray diffraction analyses. The molecular structure of this compound was compared with already published meso‐ and β‐triphenylphosphonium porphyrins but also with an unpublished X‐ray crystallographic structure of MgII 5‐triphenylphosphoniumporphine (MgP‐PPh3+,PF6–) previously obtained by electrosynthesis.

A 3D electropolymerized thin film based on an isoporphyrin and on a pyridine end-decorated molybdenum(II) halide cluster: Photoelectrochemical and impedance properties

“…Electrosynthesis of Zn and Mg meso-triarylphosphonium porphyrin were as well reported from Zn or Mg 5,10,15-triarylporphyrin indicating a nucleophilic substitution is mainly at the meso and not at the β position [32]. Furthermore, the electrochemical oxidation of pyridin-2-ylthiomeso substituted Ni(II) porphyrins afforded oxidative C-N fusion of pyridinylsubstituted porphyrins again at the meso position giving cationic and dicationic pyridinium-based products [33].…”

Recent advances in electrochemical meso- and β-functionalization of porphyrins and electrografting of diazonium porphyrins

“…of PPh3, 10 eq. of 2,6-lutidine, at Eapp = 0.70 V/SCE [41]. Very recently, Ruppert, Weiss and coworkers presented their porphyrin-tweezer target that they wanted to prepare by electrosynthesis starting with 1,3-bis(pyridin-3-ylethynyl)benzene as the dinucleophilic spacer and 10-(4-methoxyphenyl)-5,15-di-p-tolylporphyrin cation radical as the electrophile (Scheme 2A) [42].…”

“…Scheme 2. Functionalization of porphyrin monomers (A, [11,36,38,41,42]); preparation of oligomers (B, [37]); synthesis of copolymers (C, [43][44][45][46][47][48][49][50]).…”

Current Design of Mixed-Ligand Complexes of Magnesium(II): Synthesis, Crystal Structure, Thermal Properties and Biological Activity against Mycolicibacterium Smegmatis and Bacillus Kochii

“…The chemistry of alkaline-earth metal complexes is among the actively developing areas of coordination chemistry [1][2][3][4][5][6][7][8][9]. However, complexation with Mg 2+ ions often demonstrates quite different binding schemes than the corresponding compounds of IIA metals [10][11][12][13].…”