Very High Oxidation States in Organometallic Chemistry

Malischewski, Moritz

doi:10.1016/b978-0-12-820206-7.00004-4

Cited by 1 publication

(3 citation statements)

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“…[12] The heavier halides AgBr 2 and AgI 2 are known to be even less stable. [13] In the realm of organometallic chemistry, we recently found that the organosilver(III) fluoride [PPh 4 ][(CF 3 ) 3 AgF] shows an ideal combination of thermal stability and chemical reactivity, as was briefly communicated. [14] The heavier organosilver(III) halides [(CF 3 ) 3 AgX] À (X=Cl, Br, I) had been detected in solution by Eujen, Hoge and Brauer, but could not be isolated.…”

Section: Introductionmentioning

confidence: 97%

“…[1,2] This new paradigm opens a wealth of possibilities for a metal, which has been traditionally confined to a limited role as a one-electron reagent. As a result of these new findings, novel Ag III species belonging to the select class of high-valent organometallic derivatives [3] are now considered as feasible reaction intermediates. A key step in this new reactivity pattern for silver is the oxidative addition of a halocarbon, RX, to the Ag I centre to afford the oxidized RÀ [Ag III ]À X entity.…”

Section: Introductionmentioning

confidence: 99%

“…[14] The heavier organosilver(III) halides [(CF 3 ) 3 AgX] À (X=Cl, Br, I) had been detected in solution by Eujen, Hoge and Brauer, but could not be isolated. [15] Although the isolation of the [N(PPh 3 ) 2 ][(CF 3 ) 3 AgX] (X=Cl, Br) salts was later claimed, [16] only fragmentary information and insufficient data were reported. Thus, little is known about the compatibility of Ag III with the heavier halides.…”

Section: Introductionmentioning

confidence: 99%

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

Joven-Sancho

Baya

Falvello

et al. 2021

Chemistry A European J

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The involvement of silver in two-electron Ag I /Ag III processes is currently emerging. However, the range of stability of the required and uncommon Ag III species is virtually unknown. Here, the stability of Ag III towards the whole set of halide ligands in the organosilver(III) complex frame [(CF 3 ) 3 AgX] À (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 Ag III À X bonds. Our estimates were confirmed by experiment. The whole series of nonradiative halide complexes [PPh 4 ][(CF 3 ) 3 AgX] (X=F, Cl, Br, I) has been experimentally prepared and all its constituents have been isolated in pure form. The pseudohalides [PPh 4 ][(CF 3 ) 3 AgCN] and [PPh 4 ][(CF 3 ) 3 Ag(N 3 )] 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 [(CF 3 ) 3 AgX] À entities at the unimolecular level have been examined in the gas phase by multistage mass spectrometry (MS n ). The experimental detection of the two series of mixed complexes [CF 3 AgX] À and [FAgX] À arising from the corresponding parent species [(CF 3 ) 3 AgX] À demonstrate that the AgÀ X bond is particularly robust. Our experimental observations are rationalized with the aid of theoretical methods. Smooth variation with the electronegativity 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 Ag III with the heaviest halides is of particular relevance to silver-mediated or silver-catalyzed processes.

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