Dinuclear μ-fluoro cations of copper, silver and gold

Heterolysis of Dihydrogen by Silver Alkoxides and Fluorides

“…The reaction of ruthenium(II) fluorides with H 2 ,4 however, is believed to be thermodynamically driven, and silver(I) fluoride itself reacts readily with H 2 to form unstable hydrides 10. Fluoride‐bridged dinuclear cations of the group 11 metals display considerable basicity despite their overall positive charge 22. We hoped that the hard/soft acid–base mismatch23 of the Ag I F bond, and the strength of the resulting HF bond,24 would facilitate hydrogenolysis both kinetically and thermodynamically.…”

“…Complexes {[(5Dipp)Ag] 2 (μ‐O‐ t Bu)} + [BF 4 ] − ( 1 a [BF 4 ]), (5Dipp)AgF ( 2 a ), {[(5Dipp)Ag] 2 (μ‐F} + [BF 4 ] − , {[(5Dipp)Ag] 2 (μ‐H)} + [BF 4 ] − ( 3 a [BF 4 ]), and {[(5Dipp)Ag] 2 (μ‐H)} + [OTf] − ( 3 a [OTf]) have been described previously 16. 22 In this study these complexes were characterized by 1 H and, in the case of the fluorides, 19 F NMR spectroscopy. Preparations of (6Dipp)AgOTs, (6Dipp)AgOTf, (6Dipp)Ag(O‐ t ‐Pent), (7Dipp)AgOTs, and (7Dipp)Ag(O‐ t ‐Pent), beginning from published complexes, and NMR spectra of the new complexes are given in the Supporting Information.…”

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

“…The only well‐established organosilver fluorides of molecular nature reported to date, namely (SIDipp)AgF and [{(SIDipp)Ag} 2 (μ‐F)][BF 4 ], contain silver(I) centers stabilized by NHC‐ligands . The lack of precedents in silver(III) chemistry can be ascribed to the unavailability of suitable synthetic methods, which is probably related to the higher lability of silver compared to gold.…”

Carbonsäurefluoride in der Katalyse durch späte Übergangsmetalle

“…Der Ligandenaustausch von Metallhalogeniden oder ‐pseudohalogeniden (M‐X) durch Carbonsäurefluoride ist eine weitere stöchiometrische Anwendung zur Fluorierung von Übergangsmetallkomplexen. Diese Art der Reaktion, die Gruppe‐11‐Metall‐Alkoxid‐Komplexe mit einem N‐heterocyclischen Carbenligand (NHC‐Ligand) aufweist, wurde 2014 von Sadhigi und Mitarbeitern untersucht . Es wurde beschrieben, dass der Anionenaustausch zwischen Benzoylfluorid und M(O t Bu)(SIPr)‐Komplexen (M=Cu, Ag, Au; SIPr=1,3‐Bis(2,6‐diisopropylphenyl)imidazolin‐2‐yliden) die M(F)(SIPr)‐Komplexe und Benzoesäure‐ tert ‐butylester liefert (Schema ).…”