Issue 6, 2024

meso-Aryl substituents modify the electrochemical profile and palladium(ii) coordination of redox-active tripyrrin ligands

Abstract

The tripyrrin coordination motif, namely a conjugated tripyrrolic fragment of the porphyrin scaffold, is found in numerous metal complexes of oligopyrrolic macrocycles. Because of their typically limited stability, linear tripyrrins are underutilized in coordination chemistry; however, hexaalkyl-tripyrrindiones featuring the pyrrolinone termini characteristic of biopyrrin pigments have recently emerged as versatile redox-active ligands. Herein, we report the synthesis of the first example of meso-di(pentafluorophenyl) tripyrrin-1,14-dione through the demethylation of a stable 1,14-dimethoxytripyrrin precursor. The two tripyrrin ligands coordinate palladium(II) in square planar geometries in completely distinct ways: the dimethoxytripyrrin forms a cyclopalladate following C(sp3)–H bond activation at one of the methoxy groups, whereas the tripyrrindione binds as a trianionic ligand engaging an adventitious aqua ligand in hydrogen-bonding interactions. When compared to the hexaalkyl substituents of previous tripyrrindiones, the meso-aryl groups significantly alter the electrochemical profile of the Pd(II) tripyrrindione complex, shifting anodically by ∼500 mV the one-electron processes to attain the other redox states of the ligand. The formation of a ligand-based radical on the Pd(II)-bound meso-aryl tripyrrindione is confirmed by spectroelectrochemical and electron paramagnetic resonance (EPR) methods.

Graphical abstract: meso-Aryl substituents modify the electrochemical profile and palladium(ii) coordination of redox-active tripyrrin ligands

Supplementary files

Article information

Article type
Research Article
Submitted
18 Dec 2023
Accepted
05 Feb 2024
First published
12 Feb 2024
This article is Open Access
Creative Commons BY-NC license

Inorg. Chem. Front., 2024,11, 1789-1798

meso-Aryl substituents modify the electrochemical profile and palladium(II) coordination of redox-active tripyrrin ligands

I. Habenšus and E. Tomat, Inorg. Chem. Front., 2024, 11, 1789 DOI: 10.1039/D3QI02597G

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