Magnetic and Spectral Studies on Cobalt(II) and Copper(II) Salts of Methylsulfuric, Trifluoromethylsulfuric, and Paratolylsulfuric Acids

Abstract

The compounds Co(CF3SO3)2, Cu(CF3SO3)2, Co(CH3SO3)2, Cu(CH3SO3)2, Co(p-CH3C6H4SO3)2, and Cu(p-CH3C6H4SO3)2 have been prepared and infrared spectra, electronic spectra, and magnetic susceptibility studies are reported. Electronic spectral and magnetic studies have also been made on Cu(FSO3)2 and previously published data on Co(FSO3)2 are reexamined here. The studies indicate that in all salts the metal ions are hexacoordinated by oxygen atoms provided by anions acting as tridentate bridging ligands. The MO6 skeleton is significantly distorted from regular octahedral geometry for all salts with the possible exceptions of Co(FSO3)2, Co(p-CH3C6H4SO3)2, and Co(CH3SO3)2. Values of the spin–orbit coupling constants for the salts, as estimated from the magnetic studies, decrease with increasing anion basicity, suggesting a correlation between basicity and the degree of covalent character in the metal–anion bonds. In the case of the cobalt salts the interelectron repulsion parameter B also seems to decrease with increasing anion basicity.

Preparation, reactions, and characterization of trichloroselenium(IV) and trichlorotellurium(IV) sulfonates: SeCl3(XSO3) and TeCl3(XSO3) with X = CF3, CH3, and p-CH3C6H4

“…Earlier vibrational studies on sulfonate ligands provided information on ionic XS03-groups (10-12), covalently bonded monodentate -OS02X groups (13)(14)(15), and bidentate bridging and tridentate XS03 groups (16)(17)(18). Band assignments have been made assuming that the C3" local symmetry for the CS03 moiety (or tridentate XS03-group), which would be responsible for six fundamentals, three E (v,,(S03), S,,(S03), and p,(S03)) and three A (vs(S03), v(S-C), and &(SO3)) modes of ir-active vibrations, is lowered to local C, (or C,) on monodentate type Can.…”

Structural, magnetic, and spectroscopic studies of tetrakis(pyridine) complexes of iron(II) sulfonates

“…In view of the fact anhydrous salts (15,16) as well as in pyridine complexes (17). that they are the anions of relatively strong acids, they might be…”

Preparation, properties, and characterization of methanesulfonato complexes of arsenic(III), antimony (III), and bismuth(III)

“…The observed results (number of CH3SO; ions = 1) easily rule out reactions [6], [8], and [lo]. Reaction [9] can be ruled out as it has been shown earlier (reaction [2]) that the conductivity of As(S03CH3)3 in methanesulfonic acid is due to its basic ionization.…”

“…Methanesulfonates of only a few elements have been prepared in the past mainly using solvolytic reactions in methanesulfonic acid (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12). This paper describes the synthesis and characterization of compounds M(S03CH3), (M = As(III), Sb(LU), and Bi(ILI)), [ N~A s O ( S O~C H~)~] , and Na[Bi(S03CH3)4] by reaction of methanesulfonic anhydride with suitable oxides or oxosalts.…”