Stability of Ag(III) towards Halides in Organosilver(III) Complexes

The involvement of silver in two-electron AgI/AgIII processes is currently emerging. However, the range of stability of the required  and uncommon AgIII species is virtually unknown. Here, the stability of AgIII towards the whole set of halide ligands in the organosilver(III) complex frame [(CF3)3AgX]¯ (X=F, Cl, Br, I, At) is theoretically analyzed. The results obtained depend on a single factor: the nature of X. Even the softest and least electronegative halides (I and At) are found to form reasonably stable AgIII–X bonds. Our estimates were confirmed by experiment. The whole series of  nonradiative halide complexes [PPh4][(CF3)3AgX] (X=F, Cl, Br, I) has been experimentally prepared and all its constituents have been isolated in pure form. The pseudohalides [PPh4][(CF3)3AgCN] and [PPh4][(CF3)3Ag(N3)] have also been isolated, the latter being the first silver(III) azido complex. Except for the iodo compound, all the crystal and molecular structures have been established by single-crystal X-ray diffraction methods. The decomposition paths of the [(CF3)3AgX]¯ entities at the unimolecular level have been examined in the gas phase by multistage mass spectrometry (MSn). The experimental detection of the two series of mixed complexes [CF3AgX]¯ and [FAgX]¯ arising from the corresponding parent species  (CF3)3AgX]¯ demonstrate that the Ag–X bond is particularly robust. Our experimental observations are rationalized with the aid of theoretical methods. Smooth variation with the  lectronegativity of X is also observed in the thermolyses of bulk samples. The thermal stability in the solid state gradually decreases from X=F(145 °C, dec.) to X=I (78 °C, dec.) The experimentally established compatibility of AgIII with the heaviest halides is of particular relevance to silver-mediated or silver-catalyzed processes.