Homoleptic Trifluoromethyl Derivatives of Ag^I and Ag^III

Abstract

The homoleptic silver(I) compound [PPh ][CF AgCF ] (1) provides a convenient entry to the homoleptic silver(III) derivative [PPh ][Ag(CF ) ] (2). Once isolated as pure substances, these compounds exhibit marked thermal stabilities. Their structural and spectroscopic properties have been experimentally established. Moreover, their electronic structures have been calculated by theoretical methods. The electronic structure of the oxidized species [Ag(CF ) ] provides a new case of ligand-field inversion caused by the CF ligands.

The First Organosilver(III) Fluoride, [PPh4][(CF3)3AgF]

“…The involved Ag−C distance (203.6(2) pm) is, in turn, substantially shorter than that corresponding to the mutually trans CF 3 groups (Ag−C 209.8(2) pm av.). The latter value exactly coincides with the mean value observed in the homoleptic derivative [PPh 4 ][(CF 3 ) 4 Ag] . There is also excellent agreement between the structure of the [(CF 3 ) 3 AgF] − anion experimentally found in crystals of 2 and that calculated in the gas phase by theoretical methods (DFT/M06).…”

“…Based on our previous experience, the CF 3 group was selected here to stabilize Ag III . Access to the (CF 3 ) 3 Ag fragment, however, was not so easy.…”

“…In the solid state, compound 2 is appreciably less stable (dec. 145 °C; Figure S14, SI) than the homoleptic compound [PPh 4 ][(CF 3 ) 4 Ag] (dec. 188 °C) and much less so than its gold homologue [PPh 4 ][(CF 3 ) 3 AuF] (m.p. 180 °C, dec. 267 °C) .…”

Exploring the Role of Coinage Metalates in Trifluoromethylation: A Combined Experimental and Theoretical Study

“…

Despite the knownn ucleophilic nature of [M(CF 3 ) 2 ] À (M = Cu, Ag, Au) complexes, their participation in trifluoromethylation reactions of aryl halides remains unexplored.H ere, for the first time, selective accesst oa [Cu(CF 3 ) 2 ] À species is reported, whichi su biquitous in Cumediated trifluoromethylations, and we rationalize its complex mechanistic scenario as well as its behavior compared to its silver and gold congeners through ac ombination of experimental and computational approaches.Undoubtedly, over the past years, trifluoromethyl organometallic compounds of coinage metalsh ave played ak ey role as reactive intermediates in organic synthesis. [1][2][3] In this context, fundamental studies on the reactivity of ate-type complexes as nucleophiles has received little attentionb ecause, until recently,o nly well-defined( Cat)[Au(CF 3 ) 2 ]c omplexes were isolable. [4] In 2018, we reported, for the first time, not only the isolation of au nique silver salt, (Cs)[Ag(CF 3 ) 2 ], but also its high efficiency as at ransmetalating reagent in Pd-catalyzed trifluoromethylations.

…”

“…Undoubtedly, over the past years, trifluoromethyl organometallic compounds of coinage metalsh ave played ak ey role as reactive intermediates in organic synthesis. [1][2][3] In this context, fundamental studies on the reactivity of ate-type complexes as nucleophiles has received little attentionb ecause, until recently,o nly well-defined( Cat)[Au(CF 3 ) 2 ]c omplexes were isolable. [4] In 2018, we reported, for the first time, not only the isolation of au nique silver salt, (Cs)[Ag(CF 3 ) 2 ], but also its high efficiency as at ransmetalating reagent in Pd-catalyzed trifluoromethylations.…”