A Multistep Oxidative Cascade Reaction from a Naphthalenediol‐Based Pre‐Ligand to a Tetranuclear Perylenequinone‐Based Fe III Complex
Year: 2024
Type: article
Abstract: We have developed a family of dinuclear complexes using 2,7‐disubstituted 1,8‐naphthalenediol ligands that bind by molecular recognition to two neighboring phosphate diesters of the DNA backbone with the dinuclear Cu II and Ni II complexes exhibiting a severe cytotoxicity for human cancer cells. To increase the binding affinity, we intended to synthesize the corresponding dinuclear Fe III complex. Surprisingly, we obtained a tetranuclear Fe III perylene‐based complex instead of the expected dinuclear Fe III naphthalene‐based complex. In order to establish a rational and reproducible synthesis, we carefully analyzed this reaction. This revealed a multistep oxidative cascade reaction including the pre‐coordination of Fe II ions in the N 3 ‐binding pockets, the Lewis‐acid assisted MOM‐deprotection of the pre‐ligand by the pre‐oriented Fe II ions, two oxidative aromatic C−C coupling reactions, oxidation of the perylene‐based backbone and of Fe II to Fe III . The careful analysis of bond lengths, HOMA indices (harmonic oscillation model of aromaticity), FTIR and UV‐Vis‐NIR spectra supported by DFT calculations reveals the presence of an aromatic 18‐electron oxidized perylenequinone ligand backbone. In summary, a multistep cascade reaction involving in total a 10‐electron oxidation has been established for the straight‐forward synthesis of an unprecedented perylenequinone‐based ligand system.
Source: Chemistry - A European Journal
Institution: Bielefeld University
Language: English
Subfield: Oncology
Field: Medicine
Domain: Health Sciences
Open Access status: hybrid
Estimated APC paid: $4,640
Funder: Universität Bielefeld
OpenAlex ID: W4404498603