π-Lewis Base Activation of Carbonyls and Hexafluorobenzene

Mondal A, Breitwieser K, Danés S, Grünwald A, Heinemann FW, Morgenstern B, Müller F, Haumann M, Schütze M, Kass D, Ray K, Munz D (2025)

Publication Type: Journal article

Publication year: 2025

Journal

Angewandte Chemie International Edition Wiley

DOI: 10.1002/anie.202418738

Abstract

We report hitherto elusive side-on η2-bonded palladium(0) carbonyl (anthraquinone, benzaldehyde) and arene (benzene, hexafluorobenzene) palladium(0) complexes and present the catalytic hydrodefluorination of hexafluorobenzene by cyclohexene. The comparison with respective cyclohexene, pyridine and tetrahydrofuran complexes reveals that the experimental ligand binding strengths follow the order THF6H66F63-edge X-ray absorption (XAS), and X-ray photoelectron (XP) spectroscopic techniques, complemented by Density Functional Theory (DFT) calculations including energy decomposition (EDA-NOCV) and effective oxidation state (EOS) analyses. For benzene, pyridine and cyclohexene, bonding follows the donor/acceptor picture of the Dewar–Chatt–Duncanson model. In stark contrast, hexafluorobenzene, benzaldehyde and anthraquinone bind via essentially the π-channel only and thus as π-analogues of Z-acceptor ligands. This contribution elucidates the control of functional-group selectivity in palladium(0) catalysis and delineates a novel strategy to activate electron-deficient π-systems.

Authors with CRIS profile

Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Universitat de Girona ES Spain (ES) Universität des Saarlandes (UdS) DE Germany (DE) Freie Universität Berlin DE Germany (DE) Humboldt-Universität zu Berlin DE Germany (DE)

How to cite

APA:

Mondal, A., Breitwieser, K., Danés, S., Grünwald, A., Heinemann, F.W., Morgenstern, B.,... Munz, D. (2025). π-Lewis Base Activation of Carbonyls and Hexafluorobenzene. Angewandte Chemie International Edition. https://doi.org/10.1002/anie.202418738

MLA:

Mondal, Aditesh, et al. "π-Lewis Base Activation of Carbonyls and Hexafluorobenzene." Angewandte Chemie International Edition (2025).

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