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

Joven-Sancho, Daniel; Baya, Miguel; Martín, António; Orduna, Jesús; Menjón, Babil

doi:10.1002/chem.201905771

Cited by 20 publications

(34 citation statements)

References 63 publications

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“…In the latter case, the terminal F ligand forms loose [Ag]À F•••HC(sp 2 ) hydrogen bonds with the cation, as already pointed out in our previous communication. [14] The experimentally obtained structures of the [(CF 3 ) 3 AgX] À anions (X=F, Cl, Br) are invariably square-planar (Figure 3), as is usually found in d 8 metal complexes. The most relevant geometric parameters are given in Table 1, where they are compared with those corresponding to the all-organometallic [PPh 4 ][(CF 3 ) 3 AgR] compounds (R=CH 3 , [15] CF 3 ).…”

Section: Experimental Ground-state Structuresmentioning

confidence: 76%

“…[16] We have found, however, that the reaction of complex 2 with AgF in MeCN (Scheme 3) affords the fluoro-derivative [PPh 4 ][(CF 3 ) 3 AgF] (1), which is isolated as a white solid in 75 % yield. [14] This is the first organosilver(III) fluoride compound to have been prepared or even detected. Our preliminary assays demonstrated that the terminal F-ligand in compound 1 is reactive, as it readily undergoes solvolysis with H 2 O and with thiols RSH.…”

Section: Synthetic Proceduresmentioning

confidence: 98%

“…Our preliminary assays demonstrated that the terminal F-ligand in compound 1 is reactive, as it readily undergoes solvolysis with H 2 O and with thiols RSH. [14] We took further advantage of the reactivity of this unique compound.…”

Section: Synthetic Proceduresmentioning

confidence: 99%

“…[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. [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.…”

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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Section: Experimental Ground-state Structuresmentioning

confidence: 76%

Section: Synthetic Proceduresmentioning

confidence: 98%

Section: Synthetic Proceduresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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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“…[8] Pioneering work by Ritter, Li, Hartwig and Sarpong allowed for the fluorination of distinct skeletons and pointed to the capital role of elusive Ag II F or Ag III F compounds. [9,10] Most astonishing, organosilver(III) species effecting cross-coupling were authenticated by Ribas, [11] Menjón [12] and Shen [13] who accomplished CÀ C and CÀ heteroatom bond formations nurtured by aryl-Ag III catalyst I, [11] or the trifluoromethylation of thiols and arenes enabled by the anions [Ag III (F)(CF 3 ) 3 ] À II [12] and [Ag III (aryl)(CF 3 ) 3 ] À III, [13] respectively (Figure 1A). [14] From another standpoint, the fluorido-complex II is reminiscent of the long-known homoleptic anion [Ag III (CF 3 ) 4 ] À 1 [15] that pertains to the intriguing coinage metalate(III) series [M III -(CF 3 ) 4 ] À .…”

Section: Introductionmentioning

confidence: 99%

Cross‐Coupling through Ag(I)/Ag(III) Redox Manifold

Demonti

Saffon‐Merceron

Mézailles

et al. 2021

Chemistry A European J

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In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e À redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through Ag I /Ag III redox catalysis (i. e. CEL coupling), namely: i) easy Ag I /Ag III 2e À oxidation mediated by air; ii) bpy/phen ligation to Ag III ; iii) boron-to-Ag III aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-Ag III -CF 3 ] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K] + [Ag III (CF 3 ) 4 ] À (K-1), [(bpy)Ag III (CF 3 ) 3 ] (2) and [(phen)Ag III (CF 3 ) 3 ] (3), is described. The utility of 3 in crosscoupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [Ag III (aryl)(CF 3 ) 3 ] À intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.

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An Organocopper(III) Fluoride Triggering C−CF₃ Bond Formation

Joven‐Sancho,

Echeverri,

Saffon‐Merceron

et al. 2024

Angewandte Chemie

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Copper(III) fluorides are catalytically competent, yet elusive, intermediates in cross‐coupling. The synthesis of [PPh4][CuIII(CF3)3F] (2), the first stable (isolable) CuIII−F, was accomplished via chloride addition to [CuIII(CF3)3(py)] (1) yielding [PPh4][CuIII(CF3)3Cl(py)] (1.Cl), followed by treatment with AgF. The CuIII halides 1.Cl and 2 were fully characterized using nuclear magnetic resonance (NMR) spectroscopy, single crystal X‐ray diffraction (Sc‐XRD) and elemental analysis (EA). Complex 2 proved capable of forging C−CF3 bonds from silyl‐capped alkynes. In‐depth mechanistic studies combining probes, theoretical calculations, trapping of intermediate 4a ([PPh4][CuIII(CF3)3(C≡CPh)]) and radical tests unveil the key role of the CuIII acetylides that undergo facile 2e− reductive elimination furnishing the trifluoromethylated alkynes (RC≡CCF3), which are industrially relevant synthons in drug discovery, pharma and agrochemistry.

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

Cited by 20 publications

References 63 publications

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

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

Cross‐Coupling through Ag(I)/Ag(III) Redox Manifold

An Organocopper(III) Fluoride Triggering C−CF₃ Bond Formation

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

Cited by 20 publications

References 63 publications

Stability of AgIII towards Halides in Organosilver(III) Complexes

Stability of AgIII towards Halides in Organosilver(III) Complexes

Cross‐Coupling through Ag(I)/Ag(III) Redox Manifold

An Organocopper(III) Fluoride Triggering C−CF3 Bond Formation

Contact Info

Product

Resources

About

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

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

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

An Organocopper(III) Fluoride Triggering C−CF₃ Bond Formation