Silver compounds in synthetic chemistry. Part 3. 4-Tetrafluoropyridyl silver(I), AgC5F4N – A reagent for redox transmetallations with group 12–14 elements

Silver Compounds in Synthetic Chemistry. Part 8. Complexes of Perfluoroorgano Silver(I) Derivatives with 4‐Dimethylaminopyridine (DMAP)

“…[32] However, the bonding situation around silver matches all expectations. The silver-carbon length [206.8(3) pm] is short in comparison with reported values for derivatives with silver bound to perfluorinated aromatics ranging from 210.8(4) [5] to 214.7(2) pm [25] with some values found in between. [4,24] The Ag-N bond length [211.…”

“…The use of such and related derivatives as valuable synthons in transformations of inorganic compounds has been well-established during the last decade either in oxidative transmetallations [4][5][6][7] or halide substitution reactions. [2,3,8,9] Also in the field of organic synthesis, perfluoroorgano silver compounds attract more and more attention in the conversion of acid chlorides into perfluoroorgano ketones, [10,11] in the copper-mediated trifluoromethylation of aryl halides, [12,13] in C-H fluoroalkylation of differently substituted aromatic substrates, [14][15][16] or in the conversion of diazonium salts into trifluoromethyl-substituted aromatics.…”

Silver compounds in synthetic chemistry

“…Redox transmetallations of AgC 5 F 4 N and the pnicogens, phosphorus, arsenic, antimony, and bismuth Redox transmetallations of AgC 5 F 4 N and arsenic, antimony and bismuth proceed in a similar manner as described for the group 12-14 elements [5] or for AgC 6 F 5 and group 12-16 elements [4] (Eq. (1)).…”

“…Reactions described therein had in common that perfluoroorgano element compounds of group 15 elements could be prepared more or less selectively for the heavier elements in moderate to good yields (As, Sb, Bi). In a recent publication, we showed that AgC 5 F 4 N [5] has comparable oxidative properties as AgC 6 F 5 [1][2][3][4]. Additionally it has been shown by theoretical calculations [6] that the electron-withdrawing effect of the C 5 F 4 N ligand is even higher than that of the isolobal C 6 F 5 group; the 4-position is protected against unpredictable nucleophilic attack [7].…”

Alkali/coinage metals—organolithium, organocuprate chemistry

“…134 A collection of silver complexes with chiral amino-NHC ligands have also been prepared. 142 Ag(I) carbene precursors have been employed in the synthesis of the Rh(I) complexes (NHC)(diene)RhCl, in which NHC is either 1,3-bis(Dipp)imidazole-2-ylidene, 1,3-bis(Mes)imidazol-2-ylidene, 3-methyl-1-phenacylimidazol-2-ylidene or 3-methyl-1-picolylimidazol-2-ylidene and the diene is either nbd or cod. 135 The field of acetylenediide encapsulation continues to be extended.…”