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

Leung, P.C.; Aubke, F.

doi:10.1139/v84-489

Cited by 14 publications

(9 citation statements)

References 13 publications

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“…Hence a substantially new synthetic method is developed here. The failure to produce any evidence for [Fe(CO) 6 ][Sb 2 F 11 ] 2 by reductive carbonylation of either Fe(SO 3 F) 3 or FeCl 3 in liquid SbF 5 , while Ru(SO 3 F) 3 and Os(SO 3 F) 3 are cleanly converted to [M(CO) 6 ][Sb 2 F 11 ] 2 , M = Ru, Os 27 provides an important clue. Both M(SO 3 F) 3 , M = Ru, or Os, are low spin complexes and have between 300 and 80 K magnetic properties consistent with a 2 T 2g octahedral ground state. , On the other hand, both Fe(SO 3 F) 3 60 and FeCl 3 61 are high spin complexes with magnetic properties suggestive of a 6 A 1g ground state.…”

Section: Resultsmentioning

confidence: 99%

“…The failure to produce any evidence for [Fe(CO) 6 ][Sb 2 F 11 ] 2 by reductive carbonylation of either Fe(SO 3 F) 3 or FeCl 3 in liquid SbF 5 , while Ru(SO 3 F) 3 and Os(SO 3 F) 3 are cleanly converted to [M(CO) 6 ][Sb 2 F 11 ] 2 , M = Ru, Os 27 provides an important clue. Both M(SO 3 F) 3 , M = Ru, or Os, are low spin complexes and have between 300 and 80 K magnetic properties consistent with a 2 T 2g octahedral ground state. , On the other hand, both Fe(SO 3 F) 3 60 and FeCl 3 61 are high spin complexes with magnetic properties suggestive of a 6 A 1g ground state. With both metal σ-symmetry d-orbitals (dz 2 and dx 2 -y 2 ) singly occupied, reduction to Fe (II) must bring about a change in spin state before carbonylation can occur to give octahedral [Fe(CO) 6 ] 2+ with a 1 A 1g ground state.…”

Section: Resultsmentioning

confidence: 99%

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Hexakis(carbonyl)iron(II) Undecafluorodiantimonate(V), [Fe(CO)₆][Sb₂F₁₁]₂, and -Hexafluoroantimonate(V), [Fe(CO)₆][SbF₆]₂, Their Syntheses, and Spectroscopic and Structural Characterization by Single Crystal X-ray Diffraction and Normal Coordinate Analysis

et al. 1999

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Hexakis(carbonyl)iron(II) undecafluorodiantimonate(V), [Fe(CO)6][Sb2F11]2, is conveniently prepared by the oxidative carbonylation of Fe(CO)5 with XeF2 as external oxidizer in the conjugate Brønsted-Lewis superacid HF−SbF5. The colorless compound crystallizes from the reaction medium in high purity. The molecular structure is obtained by single-crystal X-ray diffraction. The cation is a regular octahedron, while the vertex-shared di-octahedral [Sb2F11]- anion is distorted from D 4 h symmetry by bending and rotational processes, due to significant interionic interactions, primarily of the F···C type. Washing of [Fe(CO)6][Sb2F11]2 with anhydrous HF results in an unusual elution of SbF5 and the quantitative conversion to hexakis(carbonyl)iron(II) hexafluoroantimonate(V) [Fe(CO)6][SbF6]2. The molecular structure of the salt shows octahedral ions with slight tetragonal distortions for the cation (elongation) and the anion (compression). Both salts are thermally stable up to 150 °C. The averaged bond distances and the vibrational wavenumbers of [Fe(CO)6]2+ are nearly identical in both compounds. The [Fe(CO)6]2+ cation, the first and so far only isolated and structurally characterized dipositive, superelectrophilic carbonyl cation formed by a 3d-metal, is further characterized by a normal coordinate analysis (NCA). The obtained force constants are compared to those of the isoelectronic molecule Cr(CO)6. Changes in π-back-bonding affect the F CO/CO and F CO/MC interaction force constants more strongly than the stretching force constants F CO and F MC. All 13 fundamentals of [Fe(CO)6]2+ are detected and assigned with the help of the data obtained from the normal coordinate analysis and density functional calculations published previously. The electronic ground state 1A1g of the [Fe(CO)6]2+ cation is established by magnetic susceptibility measurements of polycrystalline [Fe(CO)6][SbF6]2 and [Fe(CO)6][Sb2F11]2 between 2 and 300 K. The magnetic impurity formed during synthesis is identified as Fe[SbF6]2 which has iron(II) in high spin (5T2g) ground state. Consistent with a diamagnetic ground state are the single line in the 57Fe Mössbauer spectrum (i.s. = −0.003(8) mm s-1 relative to α-Fe), obtained on polycrystalline samples and the single sharp line in the 13C NMR spectrum in DF solution at 178 ppm with J (57Fe-13C) of 19.2 Hz.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Hexakis(carbonyl)iron(II) Undecafluorodiantimonate(V), [Fe(CO)₆][Sb₂F₁₁]₂, and -Hexafluoroantimonate(V), [Fe(CO)₆][SbF₆]₂, Their Syntheses, and Spectroscopic and Structural Characterization by Single Crystal X-ray Diffraction and Normal Coordinate Analysis

et al. 1999

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“…The overall process [6] involving proton bridging and proton transfer from HS03F to S2O6F2 is, however, not the only exchange process in the system. As peak area integrations (also summarized in Table 1) indicate, the "acid" ' 9~ resonance is increased at the expense of the signal attributed to S2O6F2 over the whole temperature range (318 to 198 K), with no pronounced temperature dependency recognizable.…”

Section: Results and Discussion (A) Raman Spectroscopymentioning

confidence: 99%

“…Recent representative examples with E = Au (3), Ta (3), Nb (3), Rh (4), Mn (5), Ru (6), Pt (7), Sn (8), Ge (8), Br or I (9), illustrate the wide range of this method. While S2O6F2 is the principal oxidizing agent in this reagent combination, the role of HS03F is three-fold: (a) to allow an expansion of the temperature range well beyond the boiling point of S2O6F2, 67.1°C (lo), (b) to maintain in solution and hence at the reactive site a high concentration of S03F' radicals formed by the reversible dissociation of S2O6F2 (1 I), and (c) to dissolve reaction product from the metal surface during reaction.…”

Section: Introductionmentioning

confidence: 99%

The system fluorosulfuric acid (HSO₃F) and bis(fluorosulfuryl)peroxide (S₂O₆F₂) — a solution study

Cicha¹,

Herring²,

Aubke³

1990

Can. J. Chem.

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Solutions of bis(fluorosulfuryl)peroxides, S2O6F2, in fluorosulfuric acid, HSO3F, are synthetically very useful. The nature of the solvent (HSO3F)–solute (S2O6F2 or SO3F•) interaction is probed by Raman, 1H and 19F NMR, and ESR spectroscopy, the latter focussing on the radical SO3F• formed by the dissociation of S2O6F2. Both S2O6F2 and SO3F• behave as very weak bases in HSO3F. Proton transfer between solvent and solute and SO3F exchanges are suggested on the basis of NMR and ESR measurements. The symmetry and electronic structure of the SO3F• radical are altered in HSO3F solution. A giso value of 1.97267 is obtained. The radical appears to be formed on dissolution of S2O6F2 at room temperature and persists down to 183 K. The solvent–solute interaction depends on the acid strength of the protonic solvent and addition of the base KSO3F to HSO3F leads to a loss of solubility and the separation of S2O6F2 as a second phase. Keywords: solution study in HSO3F of weak bases, Raman spectrum, ESR study in HSO3F.

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“…Bis(fluorosulfuryl)peroxide, S1O6F2, in HS0,F as solvent, on the other hand has been widely used to prepare high valent metal fluorosulfates as well ternary fluorosulfates (21)(22)(23). Due to the unavailability of similar routes in SO,CF?…”

Section: Introductionmentioning

confidence: 99%

The solvolysis of metal fluorosulfates in trifluoromethyl sulfuric acid

Mallela¹,

Sams²,

Aubke³

1985

Can. J. Chem.

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The quantitative conversion of fluorosulfates into trifluoromethyl sulfates is systematically investigated. The reaction proceeds initially according to the general equation[Formula: see text]where E is a coordinatively saturated metal or an organometallic moiety. However, the key to a quantitative substitution is the observed degradation of the SO3F group by excess HSO3CF3 and the noted observation of various volatile by-products that do not appear to interfere in the isolation of analytically pure trifluoromethyl sulfates. The fluorosulfates selected are representatives of the most common bond and coordination types—ionic or covalent with coordination through one, two, or three oxygens of the SO3F groups. The selected substrates display a fairly wide range of solubilities in HSO3F. All conversion attempts are successful except for one, that of polymeric Hg(SO3F)2, and a number of new SO3CF3 derivatives of tin, platinum, germanium, and palladium are described. The solvolysis of tin(IV) acetate in HSO3CF3 is reinvestigated and the syntheses of two other trifluoromethyl sulfuric acid derivatives, CsSO3CF3•HSO3CF3 and CH3CO2H•HSO3CF3, are described.

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

Cited by 14 publications

References 13 publications

Hexakis(carbonyl)iron(II) Undecafluorodiantimonate(V), [Fe(CO)₆][Sb₂F₁₁]₂, and -Hexafluoroantimonate(V), [Fe(CO)₆][SbF₆]₂, Their Syntheses, and Spectroscopic and Structural Characterization by Single Crystal X-ray Diffraction and Normal Coordinate Analysis

Hexakis(carbonyl)iron(II) Undecafluorodiantimonate(V), [Fe(CO)₆][Sb₂F₁₁]₂, and -Hexafluoroantimonate(V), [Fe(CO)₆][SbF₆]₂, Their Syntheses, and Spectroscopic and Structural Characterization by Single Crystal X-ray Diffraction and Normal Coordinate Analysis

The system fluorosulfuric acid (HSO₃F) and bis(fluorosulfuryl)peroxide (S₂O₆F₂) — a solution study

The solvolysis of metal fluorosulfates in trifluoromethyl sulfuric acid

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

Cited by 14 publications

References 13 publications

Hexakis(carbonyl)iron(II) Undecafluorodiantimonate(V), [Fe(CO)6][Sb2F11]2, and -Hexafluoroantimonate(V), [Fe(CO)6][SbF6]2, Their Syntheses, and Spectroscopic and Structural Characterization by Single Crystal X-ray Diffraction and Normal Coordinate Analysis

Hexakis(carbonyl)iron(II) Undecafluorodiantimonate(V), [Fe(CO)6][Sb2F11]2, and -Hexafluoroantimonate(V), [Fe(CO)6][SbF6]2, Their Syntheses, and Spectroscopic and Structural Characterization by Single Crystal X-ray Diffraction and Normal Coordinate Analysis

The system fluorosulfuric acid (HSO3F) and bis(fluorosulfuryl)peroxide (S2O6F2) — a solution study

The solvolysis of metal fluorosulfates in trifluoromethyl sulfuric acid

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Hexakis(carbonyl)iron(II) Undecafluorodiantimonate(V), [Fe(CO)₆][Sb₂F₁₁]₂, and -Hexafluoroantimonate(V), [Fe(CO)₆][SbF₆]₂, Their Syntheses, and Spectroscopic and Structural Characterization by Single Crystal X-ray Diffraction and Normal Coordinate Analysis

Hexakis(carbonyl)iron(II) Undecafluorodiantimonate(V), [Fe(CO)₆][Sb₂F₁₁]₂, and -Hexafluoroantimonate(V), [Fe(CO)₆][SbF₆]₂, Their Syntheses, and Spectroscopic and Structural Characterization by Single Crystal X-ray Diffraction and Normal Coordinate Analysis

The system fluorosulfuric acid (HSO₃F) and bis(fluorosulfuryl)peroxide (S₂O₆F₂) — a solution study