Fluorosulfates of palladium

Abstract

The syntheses of Pd(SO3F)2 and Pd(SO3F)3 by the reactions of palladium with BrOSO2F and S2O6F2 are described. Structural information on both compounds is based on infrared, Raman, diffuse reflectance, and electronic mull spectra as well as magnetic measurements from ∼300 to ∼100 K. Palladium bisfluorosulfate is found to have a polymeric structure with the fluorosulfate group acting as a tridentate ligand. As a consequence, an octahedral environment is found for Pd2+ with a 3A2g ground state, a µeff298 value of 3.39 BM and the ligand field parameter Dq = 1177 cm−1 and B = 633 cm−1. Pd(SO3F)3 is best regarded as PdII[PdIV(SO3F)6].

Synthetic and Raman spectroscopic study of the fluorosulfates of zinc, cadmium, and mercury

“…The Raman spectrum of KS03F (7) is listed for reference purposes. Also listed are reported infrared data for Pd(S03F), (4), where the electronic spectrum and the magnetic behavior indicate an undistorted environment and provide convincing evidence for the proposed structural type, so frequently encountered for metal bisfluorosulfates (1, 2, 4). Here the S03F-ion has C3" symmetry as well.…”

“…Since all attempts so far have failed to obtain single crystals suitable for an X-ray diffraction study, and since the compounds are all high melting, d o not sublime, and are completely insoluble in HS03F and other inert solvents, evidence has come from infrared spectra (2), and in case of some transition metal fluorosulfates like Pd(S03F)2 (4), from their magnetic properties and the electronic spectra. Again a regular octahedral environment for Pd(I1) is indicated (4).…”

Fluorosulfates of palladium. Part 3. The tetrakis(fluorosulfato)palladate(II) ion

“…the subsequent reduction to Pd(II)(SO,F), provides a more convenient route to this compound than the original oxidation of Pd by BrS03F, where reaction temperatures of 110°C and reaction times of two weeks are required (1). The ability of bromine to reduce Pd(1V) to Pd(I1) under these conditions also provides an explanation as to why only Pd(II)(SO,F), was formed in the original reaction (1):…”

“…In the two preceding publications in this series we have reported on the synthesis, the spectroscopic and the magnetic properties of a number of I paramagnetic palladium(I1) fluorosulfates (1,2). Most divalent palladium compounds are diamagnetic and, consistent with a dB electron configuration, have the metal in a square planar, or more rarely a five coordinate environment.…”

Complex fluoroanions in solution. VIII. Mixed anions containing fluoride and trifluoromethanesulfonate or fluorosulfate

“…Fluorosulfates and mixed fluorosulfates of the form M(FSO,),, (4)(5)(6) and MF,,(FSO,), (7,8) have been reported as well as M(FS03),,P- (9). From conductivity studies in fluorosulfonic acid the existence of the species MF,,-(FSO,),"-has been implied where M is Sb, As, and Bi (10).…”