A Versatile Silver(I) Pentafluorooxosulfate Reagent for the Synthesis of OSF₅ Compounds

Abstract

Herein, we report the preparation of silver(I) pentafluorooxosulfate from commercially available AgF and OSF 4 . The compound is surprisingly stable in a MeCN solution. Apart from that, AgOSF 5 has been stabilised by the addition of 2,2'-bipyridine ligands. Starting from solutions of the unstabilised silver(I) salt, OSF 5 complexes with Ni II , Cu I , and Cu II -centres have been obtained. In addition, AgOSF 5 has proven to be generally capable of mediating the transfer of OSF 5 groups to aryne moieties, thus furnishing a new and safe method for the preparation of OSF 5 -substituted arenes. X-ray crystal structure analysis of selected transition-metal OSF 5 compounds have revealed distorted octahedral [OSF 5 ] À anions which are extensively stabilised by hydrogen bonding.Scheme 1. Preparation of silver(I) pentafluorooxosulfate 3.

Unravelling the Role of the Pentafluoroorthotellurate Group as a Ligand in Nickel Chemistry

“…In related nickel pentafluorooxosulfate compounds, the OSF 5 ligand was also suggested to undergo dissociation upon dissolving in acetonitrile. [40] …”

“… [42] Interestingly, in the related [OSF 5 ] − anion, the S−O and S−F bonds can be easily differentiated in the crystal structure of [Cu(NCMe) 4 ][OSF 5 ], but in this case many H−F and H−O contacts are established between the [OSF 5 ] − anion not only with the coordinated MeCN ligands, but also with free acetonitrile molecules. [40] …”

Ein vielseitiges Silber(I)‐pentafluorooxosulfat‐Reagenz für die Synthese von OSF5‐Verbindungen

“…Es gelang uns, die Festkçrperstrukturen der Verbindungen 6 und 8 durch Einkristall-Rçntgenstrukturanalyse aufzuklären. [16] Verbindungen eher selten beobachtet wird. Da fünffach koordinierte Metallzentren meist eine Geometrie annehmen, die zwischen den beiden Extremen einer quadratischen Pyramide und einer trigonalen Bipyramide liegt, wurden geometrische Deskriptoren eingeführt, die eine bessere strukturelle Charakterisierung erlauben.…”

Photochemical Activation of Sulfur Hexafluoride: A Tool for Fluorination and Pentafluorosulfanylation Reactions

“…This arsenal is complemented by some more exotic emerging fluorinated motifs for which lack of almost any synthetic accessibility today including SF4-bridged motifs, -NRCF3 or -OSF5, to mention only some of these motifs. 34 SF5-compounds behave as promising analogues of CF3-motifs in drugs and other functional organic compounds like agrochemicals or liquid crystals, that connect high lipophilicity with low rotational barriers and steric bulk. Highly beneficial properties have been proposed for the SF5 group in pharmaceutically active drugs, 35,36 functional materials, 37,38 metal complexes, 38,39 biologically active compounds, 40 or for 19 F-MRI improving SNR in combination with a ultrashort echo-time (UTE).…”

“…6) In contrast to the mentioned photoredox catalytic activation of SF6 for deoxyfluorination, our approach precisely controls the local reductivity by Nphenylphenothiazine (33) as strong photoredox catalyst with an excited state potential of Eox(33*/33 •+ )=-2.5 V (vs. SCE). It is able to transfer the SF5 group from SF6 to -methyl- (34) and phenylstyrene (35) to yield 36 and 37 (Figure 8). 78 Furthermore, the vicinal fluoride anion can be abstracted to the pentafluorosulfanyated vinyl and allyl compounds 38 and 39, respectively.…”