Beyond fluorides: Extension of chemistry of divalent silver to oxo ligands

The chemistry of divalent silver has so far been limited to fluorine-based anions, such as F−, BF4-, and SbF6-, connections to oxo ligands being scarce. To elucidate the reasons beyond that, we have analyzed the electronic structures of selected hypothetical molecules containing formally Ag(II) in the oxo-ligand environment and we have compared them to AgF2 molecule. Our density functional calculations indicate that the substantial share of spin density resides on the O atoms adjacent to Ag(II) in all oxo species studied; i.e.  , Ag(II) facilitates the formation (and often subsequent elimination) of peroxo species. Nevertheless, our computations suggest that the chemistry of Ag(II) might be extended beyond the known fluoride, fluorosulfate and triflate connections, to include perchlorate (ClO4-), nitrate (NO3-), metaphosphate (PO3-), perfluoro-t-butoxo species (−OC(CF3)3) and perfluorinated ethers, such as CF3–O–CF3.

Divalent silver easily transfers the d9 hole to the p orbitals of O in majority of oxo species (such as Ag(OH)2 with the spin density illustrated here) yielding peroxides, as follows from the DFT calculations.Figure optionsDownload as PowerPoint slide