Fluorosulfates of palladium. Part 2. The hexakis(fluorosulfato)palladate (IV)ion and palladium(II) hexakis(fluorosulfato)metallates(IV)

Abstract

The synthesis of a number of compounds containing the hexakis(fluorosulfato)palladate(IV) anion and the cations Cs+, Ba2+,NO+, and ClO2+ is reported. All compounds are diamagnetic. Also reported is the synthesis of Pd[M(SO3F)6], where M = Pt(IV) and Sn(IV). Here, palladium(II) is found in a regular octahedral environment. Both compounds are paramagnetic, consistent with a 3A2g ground state. Curie–Weiss law behavior is found and ligand field parameters for the Pd(II) derivatives are reported. Vibrational spectra are reported for all new fluorosulfato complexes.

The synthesis and characterisation of hetero-bimetallic sulfonate bridged coordination polymers of the type MIISnIV(SO3X)6 with X = F or CF3

“…Subsequently the first hetero-bimetallic fluorosulfates, P~" P~'~( S O~F ) , and ~d " S n '~( S 0 3 F )~ (4), were obtained with identification relying again on magnetic susceptibility studies, ligand field and vibrational spectra. The ir spectra for the Pd(I1)-Sn(IV) complex were distinctly different from those previously reported for salts of the type M;[Sn(S03F),j, with M' = K, Cs, NO, and C10, ( 3 , and an "aniso bidentate" bridging function of the fluorosulfate group, with strong bonding to Sn(1V) and weak coordination to Pd(II), producing an octahedral environment for both metallic centers was suggested (4). The polymeric nature was deduced from the lack of solubility in strongly ionizing HS03F, which is in contrast to high solubility and weakly basic behavior found for the M;[Sn(S03F)6] salts (5) as well as for Ba[Pt(S03F),I (6).…”

“…The magnetic and spectroscopic study on the Pd"-MIV fluorosulfates and a parallel investigation of the corresponding silver(11) salts, ~g " S n ( s 0~F )~ and A g "~t ( s o , F )~ (6), suggested a magnetically dilute environment for the paramagnetic ions ~g ' + and more surprisingly pd2+, where an 3~2 , ground state is rather uncommon and only encountered in PdF3 (7)(8)(9) or related fluoro complexes. The study of Pd(II) fluorosulfate complexes suggested a closer approach to a bare pd2+ ion for M" being Sn rather than Pt or Pd (4).…”

The syntheses and vibrational spectra of tetrakis(carbonyl) palladium(II) and platinum(II) undecafluorodiantimonate(V), [Pd(CO)4][Sb2F11]2, and [Pt(CO)4][Sb2F11]2

“…HS03F, and SbF5 (18), the equipment used for reductive carbonylation reactions in HS0,F (17,22) or in a solid state -gas reaction (22), and our instrumentation to obtain vibrational spectra (18,22) have all been reported and described very recently. The synthesis of the starting material cisPt(C0)2(S03F), from Pt(SO,F), (19) and of cis-Pd(CO),(S03F)2 from Pd(SO,F), (23), is described elsewhere as well (22) …”

“…The synthesis of the corresponding palladium(I1) compound, Pd(C0)2(S03F),, from Pd(II)Pd(IV)(SO,F), (23), may be performed either in a solid -gas phase reaction according to:…”

Fluorosulfates of the noble metals. Part 6. Synthesis and magnetic properties of fluorosulfato compounds of ruthenium

“…(iii) Detailed studies had revealed unusual magnetic properties in some cases, such as Pd(I1) with a 3A2, ground state (1) and Ag(I1) in both a magnetically dilute and concentrated system (2). Interesting reactivity patterns were found in other instances, e.g.…”