Magnetic and Spectral Studies on Cobalt(II) Fluorosulfate

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.

Section: Physical Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

Arduini¹,

Garnett²,

Thompson³

et al. 1975

“…There have been a number of reports recently on the preparation and characterization of metal fluorosulfate compounds, including binary metal mono-(1,2), bis-(3-8), tris-(3,9, lo), and tetrakis-(10, I I ) fluorosulfates, chloro-and organotinfluorosulfates ( 1 [1][2][3][4][5][6][7][8][9][10][11][12][13][14], oxyfluorosulfates (1 5-17) and methylcyanide complexes of metal fluorosulfates (1 8). In most instances infrared spectra have been recorded and evidence regarding structure and bonding has been deduced from the number and energies of observed anion vibrations.…”

Section: Introductionmentioning

confidence: 99%

“…The infrared spectra of calcium, zinc, copper, tin, and cobalt bisfl~~orosulfates (3,7,8) have attempt to resolve such discrepancies in the literature and to extend the range of metal bisfluorosulfates studied, we have reexamined the spectra of a number of compounds and report for the first time the complete spectra (over the frequency range 250 to 1400 cm-') of the fluorosulfates of divalent magnesium, strontium, barium, cadmium, mercury, manganese, iron, nickel, and lead.…”

Section: Introductionmentioning

confidence: 99%

Infrared Spectra of Metal Bisfluorosulfates

Alleyne¹,

Mailer²,

Thompson³

1974

The infrared spectra, over the frequency range 250 to 1400 cm−1, of fourteen metal bisfluorosulfates are tabulated and discussed. The fluorosulfates of Fe(II), Co(II), Ni(II), Zn(II), Cd(II), Hg(II), Mg(II), and Ca(II) give simple spectra which are assigned to the fundamental modes of vibration of fluorosulfate groups of C3v symmetry. The spectra of the Mn(II), Cu(II), Ba(II), Pb(II), and Sn(II) compounds are assigned to fluorosulfate groups of reduced symmetry. The spectrum of Sr(II) fluorosulfate suggests the presence of at least two non-equivalent fluorosulfate environments in this compound. The general features of the infrared spectra of compounds containing tridentate coordinated fluorosulfate groups are summarized.

“…This means that the metal-anion coordination must involve terdentate fluorosulphate groups with ali three oxygen atoms coordinated in an equivalent manner. Thus the structure of Fe(SO,F), is presumably of the terdentate bridging type proposed for Co(SO,F), (6), and should involve a trigonal distortion of the Fe-0, octahedron. Fe(SO,F), therefore seemed an attractive compound to investigate, and this paper reports detailed measurements of its susceptibility and Mossbauer spectra over wide ranges of temperature.…”

Section: Inkrodlactionmentioning

confidence: 91%

Orbital ground state, crystal field splittings, and magnetic hyperfine interactions in iron(II) fluorosulphate

Sams¹,

Thompson²,

Tsin³

1977

Magnetic susceptibilities between 80 and 300 K and 57Fe Mössbauer parameters between 4.2 and 295 K are reported for Fe(SO3F)2. These data have been analysed via a crystal field model including spin–orbit and spin–spin coupling. The compound is trigonally distorted by an elongation along the [111] axis of the FeO6 octahedron, and the ground state is the orbital doublet [Formula: see text]. The quadrupole coupling constant e2qQ is positive, and no rhombic distortion could be detected. The electronic spectrum shows a splitting of the 5Eg excited level, presumably by a dynamic Jahn–Teller effect, and [Formula: see text] Attempts to fit a low-temperature magnetic perturbation Mössbauer spectrum using a pseudo-spin Hamiltonian were only partially successful, but suggest that the g tensor is highly anisotropic with [Formula: see text] and that the internal hyperfine field is small. Spin relaxation in Fe(SO3F)2 is fast at all temperatures down to 4.2 K and in applied magnetic fields of up to 5.0 T.