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Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity
Author(s) -
Kruppa Sebastian V.,
Groß Cedric,
Gui Xin,
Bäppler Florian,
Kwasigroch Björn,
Sun Yu,
Diller Rolf,
Klopper Wim,
NiednerSchatteburg Gereon,
Riehn Christoph,
Thiel Werner R.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901981
Subject(s) - photoexcitation , chemistry , phosphine , hydride , photodissociation , spectroscopy , crystallography , electron transfer , photochemistry , catalysis , atomic physics , physics , organic chemistry , hydrogen , quantum mechanics , excited state
The photoexcitation of a triangular silver(I) hydride complex, [Ag 3 (μ 3 ‐H)(μ 2 ‐dcpm) 3 ](PF 6 ) 2 ([ P ](PF 6 ) 2 , dcpm=bis(dicyclohexylphosphino)methane), designed with “UV‐silent” bis‐phosphine ligands, provokes hydride‐to‐Ag 3 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 [Ag 3 (μ 3 ‐H)] 2+ scaffold. This structural motif of [ P ](PF 6 ) 2 has been unequivocally verified by 1 H NMR spectroscopy in concert with DFT and X‐ray diffraction structural analysis, which revealed short equilateral Ag–Ag distances ( d AgAg =3.08 Å) within the range of argentophilic interactions. The reduced radical cation [ P ] . + exhibits strong oxophilicity, forming [ P +O 2 ] .+ ,which is a model intermediate for silver oxidation catalysis.