Transition metal fluorides

Winfield, John M.

doi:10.1016/s0022-1139(00)85276-8

Cited by 9 publications

(7 citation statements)

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“…Precise experimental structure determinations for TcF 5 are lacking at the current time, 36 and only a few rough indications are available. 33,[37][38][39] Thermochemical Stability. Computed energies for the fluorine elimination reaction TcF 7 f TcF 5 + F 2 and for homolytic bond breaking TcF 7 f TcF 6 + F are summarized in Table 3.…”

Section: Resultsmentioning

confidence: 99%

High-Valent Technetium Fluorides. Does TcF₇ Exist?

2007

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The structures and stabilities of technetium fluorides in high oxidation states have been studied quantum-chemically at density functional theory (B3LYP) and coupled-cluster (CCSD(T)) levels. The calculations indicate clearly that technetium heptafluoride, TcF7, has a good chance of existence and preparation, thus providing the first heptafluoride in the 4d series. The [TcF6]+ cation, a potential precursor, is also computed to be thermochemically stable against gas-phase elimination reactions. The problem with such highly fluorinated complexes appears thus to be mainly in difficult synthetic access under typical condensed-phase conditions. Matrix-isolation techniques or gas-phase experiments appear to be better suited as starting points.

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Section: Resultsmentioning

confidence: 99%

High-Valent Technetium Fluorides. Does TcF₇ Exist?

2007

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“…The force constants in Figure indicate that the oxo ligand tends to form bonds of higher order for group 7 and 8 complexes whereas the fluoro ligand does not–which is in agreement with Lewis structure considerations and experimental observations, and also with theoretical studies of transition metal fluoro complexes. , In order to understand the origin of this behavior, as well as the weak bonding of the oxo ligand with group 9 elements, the orbital structure of the complexes was analyzed.…”

Section: Resultsmentioning

confidence: 87%

“…Interestingly, throughout the analysis this behavior was never observed in any fluoro complex, which is consistent with the successful synthesis of six-coordinate tetragonal metal fluoro complexes with elements beyond group 8. 41 The second observation also explains the tendency of the oxo ligand to form multiple bonds, while the fluoro ligand does not. Linear combination of a p(X) and d(M) atomic orbital results in a set of orbitals where the first can be denoted "p", after its major contributor, or "π", due to its bonding character, and the second can be denoted "d" or "π*".…”

Section: ■ Resultsmentioning

confidence: 96%

“…Even though the basic theoretical explanation of the Oxo Wall concept in principle allows for the existence of six-coordinate tetragonal group 9 oxo complexes with an oxidation state of IV and higher (and consequently the existence of tetragonal group 10 oxo complexes with an oxidation state of V and higher, and so on), the answer lies in the orbital order and the reactivity of the resulting oxyl species. Interestingly, throughout the analysis this behavior was never observed in any fluoro complex, which is consistent with the successful synthesis of six-coordinate tetragonal metal fluoro complexes with elements beyond group 8 …”

Section: Resultsmentioning

confidence: 99%

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Where Is the Fluoro Wall?: A Quantum Chemical Investigation

2020

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Despite their isoelectronic properties, fluoro and oxo ligands exhibit completely different chemical behavior. Formally speaking, the first is known to exclusively form single bonds, while the latter is generally observed to form double (or even triple) bonds. The biggest difference, however, lies in what is known among inorganic chemists as the Oxo Wall: the fact that six-coordinate tetragonal transition metal oxo complexes are not observed beyond group 7 elements. While the Oxo Wall was explained a few decades ago, some questions regarding the nature of the Oxo Wall remain unanswered. For example, why do group 8 oxo complexes with high oxidation states not violate the Oxo Wall? Moreover, why are transition metal fluoro complexes observed through the whole transition metal series? In order to understand how the small difference between these two isoelectronic ligands can give rise to such different chemical behaviors, we conducted an extensive computational analysis of the geometric and electronic properties of model fluoro and oxo complexes with metals around the Oxo Wall. Among many insights into the details of the Oxo Wall, we mostly learned that the oxygen 2p orbitals are prone to meaningfully interact with transition metal d orbitals, because they match not only spatially but also energetically, while for fluorine the p orbital energies are lower to an extent that interaction with transition metal d orbitals is much reduced. This in turn implies that in those instances where the metal d orbitals principally accessible for interaction are occupied, the oxygen 2p orbitals are too exposed to be stable.

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“…Transition metal fluorides have been thoroughly studied during the last century [1,2]. Among them coinage metal fluorides recently attracted considerable attention: CuF system in the electrochemistry field [3][4][5][6], Ag-F as a potentially new route to superconductivity [7,8], and Au-F due to the unusual oxidation state of gold [9].…”

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confidence: 99%

Novel Copper Fluoride Analogs of Cuprates

Rybin,

Novoselov,

Korotin

et al. 2020

Preprint

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On the basis of the first-principles evolutionary crystal structure prediction of stable compounds in the CuF system, we predict two experimentally unknown stable phases -Cu2F5 and CuF3. Cu2F5 comprises two interacting magnetic subsystems with the Cu atoms in the oxidation states +2 and +3. CuF3 contains magnetic Cu 3+ ions forming a lattice with the antiferromagnetic coupling. We showed that some or all of Cu 3+ ions can be reduced to Cu 2+ by electron doping, as in the well known KCuF3. Significant similarities between the electronic structures calculated in the framework of DFT+U suggest that doped CuF3 and Cu2F5 may exhibit high-T c superconductivity with the same mechanism as in cuprates.

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Transition metal fluorides

Cited by 9 publications

References 151 publications

High-Valent Technetium Fluorides. Does TcF₇ Exist?

High-Valent Technetium Fluorides. Does TcF₇ Exist?

Where Is the Fluoro Wall?: A Quantum Chemical Investigation

Novel Copper Fluoride Analogs of Cuprates

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Transition metal fluorides

Cited by 9 publications

References 151 publications

High-Valent Technetium Fluorides. Does TcF7 Exist?

High-Valent Technetium Fluorides. Does TcF7 Exist?

Where Is the Fluoro Wall?: A Quantum Chemical Investigation

Novel Copper Fluoride Analogs of Cuprates

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Product

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High-Valent Technetium Fluorides. Does TcF₇ Exist?

High-Valent Technetium Fluorides. Does TcF₇ Exist?