Silver cation tagged on 5,7,12,14-tetraphenyl-6,13-diazapentacene and its dihydro-form

Kinzelmann M, Oschwald J, Elsen H, Warmbrunn V, Hauschild M, Harder S, Kivala M, Drewello T (2023)

Publication Type: Journal article

Publication year: 2023

Journal

Physical Chemistry Chemical Physics Royal Society of Chemistry

DOI: 10.1039/d2cp05929k

Abstract

The attachment of silver(i) cations to 5,7,12,14-tetraphenyl-6,13-diazapentacene and its reduced dihydro-form has been studied by electrospray ionization mass spectrometry (ESI-MS). The structure elucidation of the Ag+ complexes has been accomplished in gas-phase collision experiments in conjunction with density functional theory (DFT) calculations. The oxidized form provides a favourable cavity for the Ag+ ion, leading to the [1 : 1] complex with the highest resilience towards dissociation and severely hindering the attainment of a second molecular ligand. When the nitrogen is hydrogenated in the reduced dihydro-form, the cavity is partly blocked. This leads to a less strongly bound [1 : 1] complex ion but facilitates the attachment of a second molecular ligand to the Ag+. The resulting complex is the most stable among the [2 : 1] complexes. DFT calculations provide valuable insight into the geometries of the complex ions. Adding silver(i) to the reduced dihydro-form for cationization also induces its oxidation in solution. The oxidative dehydrogenation reaction, for which a mechanism is proposed, proceeds by first order kinetics and is markedly accelerated by day light.

Authors with CRIS profile

Marina Kinzelmann Sonderforschungsbereich 953/3 Synthetische Kohlenstoffallotrope Johannes Oschwald Lehrstuhl für Physikalische Chemie I Holger Elsen Lehrstuhl für Anorganische und Metallorganische Chemie Vera Warmbrunn Professur für Physikalische Chemie Sjoerd Harder Lehrstuhl für Anorganische und Metallorganische Chemie Thomas Drewello Professur für Physikalische Chemie

Involved external institutions

Ruprecht-Karls-Universität Heidelberg DE Germany (DE)

How to cite

APA:

Kinzelmann, M., Oschwald, J., Elsen, H., Warmbrunn, V., Hauschild, M., Harder, S.,... Drewello, T. (2023). Silver cation tagged on 5,7,12,14-tetraphenyl-6,13-diazapentacene and its dihydro-form. Physical Chemistry Chemical Physics. https://doi.org/10.1039/d2cp05929k

MLA:

Kinzelmann, Marina, et al. "Silver cation tagged on 5,7,12,14-tetraphenyl-6,13-diazapentacene and its dihydro-form." Physical Chemistry Chemical Physics (2023).

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