Conditions for stability of oxidation states derived from photo‐electron spectra and inductive quantum chemistry

Jørgensen, C.K.

doi:10.1002/zaac.19865400912

Cited by 32 publications

(3 citation statements)

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“…Likely candidates for ArF + salts have been the subject of speculation in the literature. Jørgensen suggested that [ArF] 2 [BeF 4 ] and [ArF][BF 4 ] might be stable while Frenking et al ruled out the latter salt and laid claim to [ArF][AuF 6 ] and [ArF][SbF 6 ] as being the more likely. Liebman and Allen, in a theoretical investigation, further proposed that ArF + might be “sufficiently stable to allow the probable isolation of [ArF + ][PtF 6 − ]”.…”

Section: Resultsmentioning

confidence: 99%

X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

et al. 2010

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The crystal structures of the xenon(II) salts, [XeF][SbF(6)], [XeF][BiF(6)], and [XeF][Bi(2)F(11)], have been determined for the first time, and those of XeF(2), [XeF][AsF(6)], [XeF][Sb(2)F(11)], and [XeF(3)][Sb(2)F(11)] have been redetermined with greater precision at -173 °C. The Bi(2)F(11)(-) anion, which has a structure analogous to those of the As(2)F(11)(-) and Sb(2)F(11)(-) anions, has been structurally characterized by single crystal X-ray diffraction for the first time as its XeF(+) salt. The fluorine bridge between the bismuth atoms is asymmetric with Bi---F(b) bond lengths of 2.092(6) and 2.195(6) A and a Bi---F(b)'---Bi bridge bond angle of 145.3(3)°. The XeF(+) cations interact with their anions by means of Xe---F(b)---M bridges. Consequently, the solid-state Raman spectra of [XeF][MF(6)] (M = As, Sb, Bi) were modeled as the gas-phase ion pairs and assigned with the aid of quantum-chemical calculations. Relationships among the terminal Xe-F(t) and bridge Xe---F(b) bond lengths and stretching frequencies and the gas-phase fluoride ion affinities of the parent Lewis acid that the anion is derived from are considered. The analogous krypton ion pairs, [KrF][MF(6)] (M = As, Sb, Bi) were also calculated and compared with their previously published X-ray crystal structures. The calculated cation-anion charge separations indicate that the [XeF][MF(6)] salts are more ionic than their krypton analogues and that XeF(2) is a stronger fluoride ion donor than KrF(2). The lattice energies, standard enthalpies, and free energies of formation for salts containing the NgF(+), Ng(2)F(3)(+), XeF(3)(+), XeF(5)(+), Xe(2)F(11)(+), and XeOF(3)(+) (Ng = Ar, Kr, Xe) cations were estimated using volume-based thermodynamics (VBT) based on crystallographic and estimated ion volumes. These estimated parameters were then used to predict the stabilities of noble-gas salts. VBT is used to examine and predict the stabilities of, inter alia, the salts [XeF(m)][Sb(n)F(5n+1)] and [XeF(m)][As(n)F(5n+1)] (m = 1, 3; n = 1, 2). VBT also confirms that XeF(+) salts are stable toward redox decomposition to Ng, F(2), and MF(5) (M = As, Sb), whereas the isolable krypton compounds and the unknown ArF(+) salts are predicted to be unstable by VBT with the ArF(+) salts being the least stable.

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Section: Resultsmentioning

confidence: 99%

X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

et al. 2010

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“…While the early 3d metals can readily form complexes in which the oxidation-state of the metal center is equal to the corresponding group number, it is recognized that high-oxidation-state 3d metal species are, in general, less stable than their 4d and 5d congeners. − The situation can be discerned from the known highest oxidation states of late 3d metals, which are lower than the corresponding group numbers and also lower than those of their heavier congeners . For example, the heavier group 8 metals Ru(VIII) and Os(VIII) can form binary oxides of the form MO 4 , whereas FeO 4 is unknown and Fe(VI), as in [FeO 4 ] 2– , is the highest oxidation state observed for Fe. , For the group 9 metals, while Ir(IX) and Rh(VI) species are known, , Co(V), as in [Co(1-norbornyl) 4 ][BF 4 ], , represents the highest oxidation state of this element.…”

Section: Challenges In the Stabilization Of High-oxidation-state 3d M...mentioning

confidence: 99%

High-Oxidation-State 3d Metal (Ti–Cu) Complexes withN-Heterocyclic Carbene Ligation

et al. 2018

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High-oxidation-state 3d metal species have found a wide range of applications in modern synthetic chemistry and materials science. They are also implicated as key reactive species in biological reactions. These applications have thus prompted explorations of their formation, structure, and properties. While the traditional wisdom regarding these species was gained mainly from complexes supported by nitrogen- and oxygen-donor ligands, recent studies with N-heterocyclic carbenes (NHCs), which are widely used for the preparation of low-oxidation-state transition metal complexes in organometallic chemistry, have led to the preparation of a large variety of isolable high-oxidation-state 3d metal complexes with NHC ligation. Since the first report in this area in the 1990s, isolable complexes of this type have been reported for titanium(IV), vanadium(IV,V), chromium(IV,V), manganese(IV,V), iron(III,IV,V), cobalt(III,IV,V), nickel(IV), and copper(II). With the aim of providing an overview of this intriguing field, this Review summarizes our current understanding of the synthetic methods, structure and spectroscopic features, reactivity, and catalytic applications of high-oxidation-state 3d metal NHC complexes of titanium to copper. In addition to this progress, factors affecting the stability and reactivity of high-oxidation-state 3d metal NHC species are also presented, as well as perspectives on future efforts.

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“…The discovery of a short-lived +3 oxidation state of Hg in 1976, generated through electrochemical reduction [3], led to the search of its +4-oxidation state, which is expected to be more stable than the +3-oxidation state, because it has the same electronic configuration (5d 8 ) as the very stable Au 3+ cation [4]. Fifteen years after it was theoretically predicted [5][6], HgF 4 was synthesized under cryogenic conditions in rare gas matrices in 2007 [7].…”

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confidence: 99%

Realization of the Zn³⁺ oxidation state

et al. 2021

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Conditions for stability of oxidation states derived from photo‐electron spectra and inductive quantum chemistry

Cited by 32 publications

References 42 publications

X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

High-Oxidation-State 3d Metal (Ti–Cu) Complexes withN-Heterocyclic Carbene Ligation

Realization of the Zn³⁺ oxidation state

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Conditions for stability of oxidation states derived from photo‐electron spectra and inductive quantum chemistry

Cited by 32 publications

References 42 publications

X-ray Crystal Structures of [XeF][MF6] (M = As, Sb, Bi), [XeF][M2F11] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

X-ray Crystal Structures of [XeF][MF6] (M = As, Sb, Bi), [XeF][M2F11] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

High-Oxidation-State 3d Metal (Ti–Cu) Complexes withN-Heterocyclic Carbene Ligation

Realization of the Zn3+ oxidation state

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X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

Realization of the Zn³⁺ oxidation state