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

Abstract

The reduction of ternary fluorosulfato complexes of palladium(IV) like cesium hexakis(fluorosulfato)palladate(IV) by bromine in liquid sulfur dioxide at room temperature or at slightly elevated temperatures results in the formation of cesium tetrakis(fluorosulfato)palladate(II), according to:[Formula: see text]In contrast to all previously reported palladium(II) fluorosulfato derivatives, Pd2+ is found in a square planar environment resulting in diamagnetism.

Coordinated trifluoromethanesulfonate and fluorosulfate

“…Oxidation of gold with excess liquid BrS03F forms Au(FS03)3, while addition of Br2 extends the synthesis to generate Au(FS03)4".185 Likewise, Pd metal with BrS03F or S206F2 generates Pd(FS03)2 and Pd(FS03)3, the former polymeric with tridentate FS03", the latter best regarded as Pdn[PdIV(FS03)6] with unidentate FS03V3 Reduction of Pd(0S02F)62~by Br2 in liquid S02 yields BrS03F and square-planar, diamagnetic Pd(0S02F)42-. 186 Although they do not bear directly on the title of this subsection, it is noted that some cases of insertion of the Lewis acid S03 into M-F bonds to form M-0S02F complexes have appeared. Cr02F2 with S03 gives Cr02(S03F)2,187 while the like reaction with UFe in the gas phase or in CFC13 solution yields UF2(S03F)3;188 like reactions with XeFe and CrF5 are known.189,190 4.…”