Silver cation tagged on 5,7,12,14-tetraphenyl-6,13-diazapentacene and its dihydro-form
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...
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| Main Authors: | , , , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
23 May 2023
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| In: |
Physical chemistry, chemical physics
Year: 2023, Volume: 25, Issue: 22, Pages: 15382-15390 |
| ISSN: | 1463-9084 |
| DOI: | 10.1039/D2CP05929K |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/D2CP05929K Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2023/cp/d2cp05929k 
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| Author Notes: | Marina Kinzelmann, Johannes Oschwald, Holger Elsen, Vera Warmbrunn, Miriam Hauschild, Sjoerd Harder, Milan Kivala and Thomas Drewello |
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| 520 | |a 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. | ||
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