| Affiliation: | 1. Department of Chemistry, Technische Universität Kaiserslautern (TUK), Erwin-Schrödinger. Str. 52, 67663 Kaiserslautern, Germany;2. Department of Chemistry, Technische Universität Kaiserslautern (TUK), Erwin-Schrödinger. Str. 52, 67663 Kaiserslautern, Germany These authors contributed equally to this work.;3. Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131 Karlsruhe, Germany;4. Department of Physics, Technische Universität Kaiserslautern (TUK), Erwin-Schrödinger. Str. 46, 67663 Kaiserslautern, Germany |
| Abstract: | The photoexcitation of a triangular silver(I) hydride complex, [Ag3(μ3-H)(μ2-dcpm)3](PF6)2 ([ P ](PF6)2, dcpm=bis(dicyclohexylphosphino)methane), designed with “UV-silent” bis-phosphine ligands, provokes hydride-to-Ag3 single and double electron transfer. The nature of the electronic transitions has been authenticated by absorption and photodissociation spectroscopy in parallel with high-level quantum-chemical computations utilizing the GW method and Bethe–Salpeter equation (GW-BSE). Specific photofragments of mass-selected [ P ]2+ ions testify to charge transfer and competing pathways resulting from the unique [Ag3(μ3-H)]2+ scaffold. This structural motif of [ P ](PF6)2 has been unequivocally verified by 1H NMR spectroscopy in concert with DFT and X-ray diffraction structural analysis, which revealed short equilateral Ag–Ag distances (dAgAg=3.08 Å) within the range of argentophilic interactions. The reduced radical cation [ P ] . + exhibits strong oxophilicity, forming [ P +O2] .+ ,which is a model intermediate for silver oxidation catalysis. |
