The synthesis and characterisation of the trifluoromethylsulfates of silver(II) and gold(III)

Abstract

The new trifluoromethylsulfates Ag(SO3CF3)2 and Au(SO3CF3)3, as well as the compound Cs[Au(SO3CF3)4], are synthesised by the solvolysis of the corresponding fluorosulfates in an excess of trifluoromethyl sulfuric acid. The resulting compounds are characterised by their vibrational spectra and, in the case of Ag(SO3CF3)2, also by esr.

Silver(II) Fluorosulfate: A Thermally Fragile Ferromagnetic Derivative of Divalent Silver in an Oxa‐Ligand Environment

“…[5] www.eurjic. Our own results confirmed the existence of these salts; [11] however, we note that they cannot be formed in a direct reaction between the corresponding pseudobinary fluorosulfates, see for example Equation (6). (6) This is due to a lack of thermal stability of the Ag-(SO 3 F) 2 precursor (see next section).…”

“…Indeed, theoretical DFT calculations predict that Ag II is capable of transferring the hole from its 4d 9 set to the 2p band of oxygen in many pseudobinary inorganic connections in the gas phase. [3] Nevertheless, several thermodynamically metastable derivatives of Ag II in the solid state with oxygen in the first coordination sphere of a metal have been reported, notably Ag II [Ag III O 2 ] 2 , [4] Ag II (SO 3 F) 2 , [5] Ag II -(SO 3 CF 3 ) 2 , [6] AgSO 4 [7] and Ag II (pz) 2 (S 2 O 8 ), in which pz = pyrazine. [8] The electronic and magnetic properties of oxa derivatives of Ag II are often surprising due to substantial 4d(Ag)-2p(O) orbital mixing, which vastly exceeds the one seen for analogous Cu II oxide derivatives.…”

“…In consequence, Ag II -[Ag III O 2 ] 2 is supposedly metallic [4] whereas AgSO 4 shows an unusually strong antiferromagnetic (AFM) coupling, which persists up to the temperature of thermal decomposition of this compound. [7] The remaining Ag II (SO 3 F) 2 [5] and Ag II (SO 3 CF 3 ) 2 [6] were only partially characterized in the previous literature reports: (i) limited data is available on the positions of IR bands; (ii) the value of the Curie temperature for ferromagnetic Ag II (SO 3 F) 2 was initially given as 20 K [5] but was then inconsistently reported as 40 K elsewhere. [9] Crystal structures and other important properties of this compound were not studied.…”

Hexafluoro antimonates(V) of divalent metals, synthesis and properties

“…Argentic oxide, Ago, represents a precedent, according to neutron diffraction studies on this compound (31). The black-brown color, also found for the recently reported oxides Ag203 (32) and Ag3O4 (33), is seemingly common to binary oxides and oxy salts of di-or trivalent silver, e.g., the sulfonates Ag(S03F)2 (20) or Ag(S03CF3)2 (34), and may possibly be due to a charge transfer transition (35). On the other hand, alkali metal salts containing the [AgF4]-ion are reported to be yellow (31,36), while AgF2 and many Ag(I1) fluoro derivatives are blue (37), just like a-Ag(SbF6), ( 14 We are not aware of any other valence isomeric pair of the Ag(I1) vs. Ag(I)Ag(III) type.…”

“…The same structural type is reported for a-Ag(SbF6)2 (14) and implicitly also for Ni (SbF6)2 (1 1). From a comparison of the Dq and B values for the two Pd(I1) compounds, it appears that in this case the tridentate SbF6-group ranks slightly higher in both the spectrochemical and nephelauxetic ligand series (34) The infrared spectra obtained for Ni(SbF6)2, Pd(SbF6)2, C U ( S~F~)~, and P-Ag(SbF6)2, together with the Raman spectra for the latter two compounds, are summarized in Tables 1 and 2. Also included are the previously reported Raman spectra for Ni(SbF6)2 (1 1) and c~-A g ( s b F~)~ (14) as well as an approximate band description, also proposed previously (1 1).…”