Results
Title

Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity.

Authors

Kruppa, Sebastian V.; Groß, Cedric; Gui, Xin; Bäppler, Florian; Kwasigroch, Björn; Sun, Yu; Diller, Rolf; Klopper, Wim; Niedner‐Schatteburg, Gereon; Riehn, Christoph; Thiel, Werner R.

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.

Subjects

CHARGE transfer; BETHE-Salpeter equation; HYDRIDES; CHARGE exchange; SILVER; SILVER ions

Publication

Chemistry - A European Journal, 2019, Vol 25, Issue 48, p11269

ISSN

0947-6539

Publication type

Academic Journal

DOI

10.1002/chem.201901981