Application of ⁶¹Ni Mössbauer spectroscopy to chemical problems

Using the possibility to produce Co-61 sources at the MAinz MIcrotron, Ni-61 Mossbauer spectroscopy was applied to different kinds of chemical problems. Measurements of isomer shifts and V-zz values in some common compounds and compounds with unusual chemical bonding for comparison with band structure calculations, measurement of Ni-61 Mossbauer parameters in model compounds for hydrogenase and dehydrogenase with an active [NiS4] centre, and study of novel binary NiF3 compounds at helium temperature are presented

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

Organosilver(III) fluoride complexes have been assigned a key role in different fluorination processes. To the best of our knowledge, however, none of them seem to have been isolated or even detected thus far. Here we report on the successful synthesis of the trifluoromethyl derivative [PPh4][(CF3)3AgF], which has been isolated in high yield. The thermodynamic stability of the Ag−F bond is shown by calculation and demonstrated by multistage mass spectrometry (MSn) under collision‐induced dissociation (CID) conditions. Nevertheless, the substantial elongation found in the Ag−F bond (X‐ray) is correlated with a marked nucleophilic character of the terminal F ligand. This Ag−F bond is, in fact, quite reactive: it suffers hydrolysis and is also solvolyzed by thiols.This work was supported by the Spanish MICIU/FEDER (Project PGC2018‐094749‐B‐I00) and the Gobierno de Aragón (Group E17_R17). The Instituto de Biocomputación y Física de Sistemas Complejos (BIFI) and the Centro de Supercomputación de Galicia (CESGA) are acknowledged for allocation of computational resources. D.J.‐S. also thanks the Spanish MICIU for a grant (BES‐2016‐078732).Peer reviewe

Preparation and NMR spectra of the (trifluoromethyl)argentates(III) [Ag(CF3)(n)X(4-n)](-), with X=CN (n=1-3), CH3, C=CC6H11, Cl, Br (n=2, 3), and I (n=3), and of related silver(III) compounds. Structures of [PPh(4)][trans-Ag(CF3)(2)(CN)(2)] and [PPh(4)][Ag(CF3)(3)(CH3)]

Eujen R, Hoge B, Brauer DJ. Preparation and NMR spectra of the (trifluoromethyl)argentates(III) [Ag(CF3)(n)X(4-n)](-), with X=CN (n=1-3), CH3, C=CC6H11, Cl, Br (n=2, 3), and I (n=3), and of related silver(III) compounds. Structures of [PPh(4)][trans-Ag(CF3)(2)(CN)(2)] and [PPh(4)][Ag(CF3)(3)(CH3)]. INORGANIC CHEMISTRY. 1997;36(7):1464-1475