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RuF6 does not oxidise XeF6 to xenon(VIII); F2 is evolved and only xenon(VI) salts form, one of them new

Can RuF6, a strong one-electron oxidiser of low Lewis acidity, oxidise XeF6 to a xenon(VIII) fluoride species such as a [XeF7]+ salt or XeF8?

Source: Failed Attempts at Oxidation of XeF6: Synthesis and Characterization of [Xe2F11][RuF6] (doi:10.1021/acs.inorgchem.6c02072). Path record: acs-xef6-path.json. Headline outcome negative-not-achievable. At every ratio and temperature tried, F2 evolved and only xenon(VI) salts formed: the new [Xe2F11][RuF6] with excess XeF6, the known [XeF5][RuF6] at 1:1, and [XeF5]+ oligofluoridoruthenates with excess RuF6. So, why does RuF6 fail to oxidize XeF6? Well, it may be that our reaction conditions are not right, yet. ... Under the conditions investigated by us so far, we only observe F2 elimination and no evidence of any Xe(VIII) compound. All graphs · Back to the pilot

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A discourse graph breaks a piece of research into typed one-sentence nodes and draws how they bear on one another. The grammar is that of Discourse Graphs (Chan and Akamatsu). Read each graph left to right: a question, the experiments that addressed it, the results they produced, and the hypothesis every result is drawn against.

QUE Question
What the work set out to answer.
HYP Hypothesis
The answer the authors expected. Every result earns one edge against it.
EXP Experiment
One attempt at the question: a trial arm, an assay, a survey, an analysis.
RES Result
One finding from an experiment, with where in the source it comes from.
ISS Issue
An open question or untried branch the work leaves for someone else.
addresses
An experiment addresses the question.
produces
An experiment produces a result.
supports
A positive result that backs the hypothesis.
opposes
A negative result that counts as evidence against the hypothesis, or a refutation of an earlier claim.
informs
A partial or mixed result that bears on the hypothesis without settling it.
consistent with
A negative or inconclusive result that does not count either way: no positive control passed, or there is no sensitivity or power statement, so the absence of an effect cannot be told from a measurement that failed.
relation
A thin dotted line: a link the source itself states between two experiments, such as one being derived from another.

A dashed box marks a result the rule above counts as uninformative, or an issue. In the drawing, click a node to jump to its text below.

The graph

Read left to right. The question (QUE) is addressed by 3 experiments (EXP), each of which produces results (RES), and each result bears on the hypothesis (HYP) with one of four edges. 7 support it, 0 oppose it, 1 inform it, and 5 are merely consistent with it because the informativeness rule would not count them as evidence either way. Click a node to jump to its full text below.

Discourse graph of RuF6 does not oxidise XeF6 to xenon(VIII); F2 is evolved and only xenon(VI) salts form, one of them new que addresses acs-xef6-oxidation-attempts acs-xef6-oxidation-attempts produces acs-xef6-oxidation-attempts--condition-excess-xef6-ahf acs-xef6-oxidation-attempts--condition-excess-xef6-ahf consistent-with hyp acs-xef6-oxidation-attempts produces acs-xef6-oxidation-attempts--condition-excess-xef6-neat acs-xef6-oxidation-attempts--condition-excess-xef6-neat consistent-with hyp acs-xef6-oxidation-attempts produces acs-xef6-oxidation-attempts--condition-equimolar-ahf acs-xef6-oxidation-attempts--condition-equimolar-ahf consistent-with hyp acs-xef6-oxidation-attempts produces acs-xef6-oxidation-attempts--condition-excess-ruf6-ahf acs-xef6-oxidation-attempts--condition-excess-ruf6-ahf consistent-with hyp acs-xef6-oxidation-attempts produces acs-xef6-oxidation-attempts--condition-low-temperature-ahf acs-xef6-oxidation-attempts--condition-low-temperature-ahf consistent-with hyp acs-xef6-oxidation-attempts produces acs-xef6-oxidation-attempts--f2-evolved acs-xef6-oxidation-attempts--f2-evolved supports hyp que addresses acs-xef6-thermodynamics acs-xef6-thermodynamics produces acs-xef6-thermodynamics--xef7-ruf6-feasible acs-xef6-thermodynamics--xef7-ruf6-feasible supports hyp acs-xef6-thermodynamics produces acs-xef6-thermodynamics--xef7-unstable-to-f2 acs-xef6-thermodynamics--xef7-unstable-to-f2 supports hyp acs-xef6-thermodynamics produces acs-xef6-thermodynamics--fluoride-ion-affinities acs-xef6-thermodynamics--fluoride-ion-affinities supports hyp acs-xef6-thermodynamics produces acs-xef6-thermodynamics--why-it-fails acs-xef6-thermodynamics--why-it-fails informs hyp que addresses acs-xef6-xe2f11-ruf6 acs-xef6-xe2f11-ruf6 produces acs-xef6-xe2f11-ruf6--crystal-structure acs-xef6-xe2f11-ruf6--crystal-structure supports hyp acs-xef6-xe2f11-ruf6 produces acs-xef6-xe2f11-ruf6--cation-geometry acs-xef6-xe2f11-ruf6--cation-geometry supports hyp acs-xef6-xe2f11-ruf6 produces acs-xef6-xe2f11-ruf6--vibrational-spectra acs-xef6-xe2f11-ruf6--vibrational-spectra supports hyp acs-xef6-thermodynamics informs acs-xef6-oxidation-attempts acs-xef6-xe2f11-ruf6 wasDerivedFrom acs-xef6-oxidation-attempts: the compound is the product of the failed oxidation with excess XeF6 ISS · open questions and untried branches this path leaves behind QUE · negative-not-achievable Can RuF6, a strong one-electron oxidiser of low Lewis acidity, oxidise XeF6 to a xenon(VIII) fluoride species such as a [XeF7]+ salt or XeF8? Can RuF6, a strong one-electron oxidiser of low Lewis acidity, oxidise XeF6 to a xenon(VIII) fluoride species such as a [XeF7]+ salt or XeF8? HYP Oxidise XeF6 with RuF6 in anhydrous HF to a xenon(VIII) fluoride species, XeF8 or a [XeF7]+ salt, which no fluoride- only route has ever produced. RuF6 is, with [KrF]+ and [NiF3]+, one of only three oxidisers able to oxidise BrF5 to [BrF6]+, and it is far less Lewis acidic than the two cations, so it should not… Oxidise XeF6 with RuF6 in anhydrous HF to a xenon(VIII) fluoride species, XeF8 or a [XeF7]+ salt, which no fluoride-only route has ever produced. RuF6 is, with [KrF]+ and [NiF3]+, one of only three oxidisers able to oxidise BrF5 to [BrF6]+, and it is far less Lewis acidic than the two cations, so it should not simply abstract fluoride from XeF6 as they do EXP · inconclusive-no-positive-control RuF6 and XeF6 at five ratio and temperature conditions evolve F2 and give only xenon(VI) salts RuF6 and XeF6 at five ratio and temperature conditions evolve F2 and give only xenon(VI) salts RES · inconclusive-no-positive-control Does RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 1:2 (excess XeF6), anhydrous HF (0.3 mL), thawed from 77 K… Does RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 1:2 (excess XeF6), anhydrous HF (0.3 mL), thawed from 77 K to room temperature? RES · inconclusive-no-positive-control Does RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 1:2 (excess XeF6), none (neat), room temperature? Does RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 1:2 (excess XeF6), none (neat), room temperature? RES · inconclusive-no-positive-control Does RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 1:1, anhydrous HF (0.3 mL), thawed from 77 K to room… Does RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 1:1, anhydrous HF (0.3 mL), thawed from 77 K to room temperature? RES · inconclusive-no-positive-control Does RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 2:1 or larger excess of RuF6, anhydrous HF, thawed… Does RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 2:1 or larger excess of RuF6, anhydrous HF, thawed from 77 K to room temperature? RES · inconclusive-no-positive-control Does RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 as above, anhydrous HF, -78 degrees C? Does RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 as above, anhydrous HF, -78 degrees C? RES · positive Is the gas evolved on mixing RuF6 and XeF6 fluorine? Is the gas evolved on mixing RuF6 and XeF6 fluorine? EXP · partial Thermodynamic estimates say a [XeF7][RuF6] salt may be stable, so the failure is not explained Thermodynamic estimates say a [XeF7][RuF6] salt may be stable, so the failure is not explained RES · positive Would a [XeF7][RuF6] salt be thermodynamically feasible from XeF8 and RuF5? Would a [XeF7][RuF6] salt be thermodynamically feasible from XeF8 and RuF5? RES · positive Is the free [XeF7]+ cation stable to loss of F2? Is the free [XeF7]+ cation stable to loss of F2? RES · positive What are the fluoride ion affinities of the species involved, with and without an HF solvent model? What are the fluoride ion affinities of the species involved, with and without an HF solvent model? RES · partial Why does RuF6 fail to oxidise XeF6, at least under these conditions? Why does RuF6 fail to oxidise XeF6, at least under these conditions? EXP · positive [Xe2F11][RuF6], a new xenon(VI) salt, characterised by single-crystal X-ray diffraction (CCDC 2477117), Raman, IR and periodic DFT [Xe2F11][RuF6], a new xenon(VI) salt, characterised by single-crystal X-ray diffraction (CCDC 2477117), Raman, IR and periodic DFT RES · positive What is the crystal structure of the colourless product from RuF6 with excess XeF6? What is the crystal structure of the colourless product from RuF6 with excess XeF6? RES · positive How does the [Xe2F11]+ cation in the ruthenium salt compare with the Au, Sb and V salts? How does the [Xe2F11]+ cation in the ruthenium salt compare with the Au, Sb and V salts? RES · positive Do the Raman and IR spectra of the product match the calculated spectrum of [Xe2F11][RuF6]? Do the Raman and IR spectra of the product match the calculated spectrum of [Xe2F11][RuF6]? ISS · open-question Is [XeF7]+ formed transiently and lost by F2 elimination, or never formed at all under these conditions? Is [XeF7]+ formed transiently and lost by F2 elimination, or never formed at all under these conditions? ISS · open-question Would a solvent other than aHF, or a different counter-anion, change the outcome, given that the salt also forms neat? Would a solvent other than aHF, or a different counter-anion, change the outcome, given that the salt also forms neat? ISS · proposed-by-authors Find conditions under which [XeF7]+ survives long enough to be trapped as an ionic solid, since the thermodynamic estimates do not rule out [XeF7][RuF6]. Find conditions under which [XeF7]+ survives long enough to be trapped as an ionic solid, since the thermodynamic estimates do not rule out [XeF7][RuF6]. ISS · proposed-by-authors Establish redox potentials or a Galvanic series for anhydrous HF. Establish redox potentials or a Galvanic series for anhydrous HF. ISS · inferred-by-ingest A solvent other than anhydrous HF, or a Lewis acid additive, given that aHF raises the oxidising power of F2 toward NF3 only with AsF5 or SbF5 present. A solvent other than anhydrous HF, or a Lewis acid additive, given that aHF raises the oxidising power of F2 toward NF3 only with AsF5 or SbF5 present.
  • supports positive finding
  • opposes informative negative, or refutation
  • informs partial finding
  • consistent with inconclusive or uninformative: no positive control passed, or no sensitivity statement
  • thin grey a relation the record itself states between two attempts
  • dashed box a result the informativeness rule marks uninformative, or an issue

The grammar is that of Discourse Graphs (Chan and Akamatsu): QUE, HYP, EXP, RES and ISS nodes with supports, opposes and informs edges. Every node and edge is derived from fields already in the Negative-Results Record; the edge a finding earns is decided by its outcomeClass and informativeness. Issues (ISS) hang below the graph as a strip: the open questions and untried branches the path leaves for someone else to pick up.

Nodes

Question and hypothesis

QUE
Can RuF6, a strong one-electron oxidiser of low Lewis acidity, oxidise XeF6 to a xenon(VIII) fluoride species such as a [XeF7]+ salt or XeF8?
HYP
Oxidise XeF6 with RuF6 in anhydrous HF to a xenon(VIII) fluoride species, XeF8 or a [XeF7]+ salt, which no fluoride-only route has ever produced. RuF6 is, with [KrF]+ and [NiF3]+, one of only three oxidisers able to oxidise BrF5 to [BrF6]+, and it is far less Lewis acidic than the two cations, so it should not simply abstract fluoride from XeF6 as they do

Experiments (3 attempts)

NodeAttemptTypeHeadlineJSON
EXPRuF6 and XeF6 at five ratio and temperature conditions evolve F2 and give only xenon(VI) salts
Excess XeF6 (neat or in aHF): [Xe2F11][RuF6] and F2. Equimolar: [XeF5][RuF6] and F2. Excess RuF6: F2, RuF5 and [XeF5]+ oligofluoridoruthenates, not quantified. At -78 degrees C the same products, more slowly. the most intense Raman bands of [XeF7]+ were quantum-chemically predicted at 588, 647 and 503 cm-1 and were not present.		wet-labinconclusive-no-positive-controlrecord
EXPThermodynamic estimates say a [XeF7][RuF6] salt may be stable, so the failure is not explained
[XeF5][RuF6] overall -611 (CP) / -368 kJ/mol; [XeF7][RuF6] overall -572 (CP) / -138 kJ/mol, 'which indicates that [XeF7][RuF6] would be a feasible compound' XeF8 formation enthalpy about -172 kJ/mol but unstable to F2 loss by about 93 kJ/mol at 0 K; [XeF7]+ unstable to F2 loss by about 191 kJ/mol at 0 K (Grant et al. 2010); packing into a solid may stabilise it no redox potentials or Galvanic series exist for anhydrous HF; the authors leave their calculation to others		computationalpartialrecord
EXP[Xe2F11][RuF6], a new xenon(VI) salt, characterised by single-crystal X-ray diffraction (CCDC 2477117), Raman, IR and periodic DFT
[Xe2F11][RuF6], mu-fluorido(bis(pentafluoridoxenonium(VI)) hexafluoridoruthenate(V) crystallises in P2_1/n (no. 14), a = 8.4517, b = 8.9602, c = 15.4691 A, beta = 95.392 degrees, V = 1166.27 A3, Z = 4 at 100 K, isotypic with the V and Sb salts; one-dimensional strands along a.		wet-labpositiverecord

Results (13 findings)

NodeFindingIdOutcome and informativenessEdgeJSON
RESDoes RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 1:2 (excess XeF6), anhydrous HF (0.3 mL), thawed from 77 K to room temperature?
target: xenon(VIII) fluoride species: [XeF7]+ salt or XeF8; xenon oxidation state of the isolated product = VI		condition-excess-xef6-ahf
in acs-xef6-oxidation-attempts		inconclusive-no-positive-control
uninformative
no positive control; no negative control; no sensitivity or power statement		consistent-with HYPrecord
RESDoes RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 1:2 (excess XeF6), none (neat), room temperature?
target: xenon(VIII) fluoride species: [XeF7]+ salt or XeF8; xenon oxidation state of the isolated product = VI		condition-excess-xef6-neat
in acs-xef6-oxidation-attempts		inconclusive-no-positive-control
uninformative
no positive control; no negative control; no sensitivity or power statement		consistent-with HYPrecord
RESDoes RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 1:1, anhydrous HF (0.3 mL), thawed from 77 K to room temperature?
target: xenon(VIII) fluoride species: [XeF7]+ salt or XeF8; xenon oxidation state of the isolated product = VI		condition-equimolar-ahf
in acs-xef6-oxidation-attempts		inconclusive-no-positive-control
uninformative
no positive control; no negative control; no sensitivity or power statement		consistent-with HYPrecord
RESDoes RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 2:1 or larger excess of RuF6, anhydrous HF, thawed from 77 K to room temperature?
target: xenon(VIII) fluoride species: [XeF7]+ salt or XeF8; xenon oxidation state of the isolated product = VI		condition-excess-ruf6-ahf
in acs-xef6-oxidation-attempts		inconclusive-no-positive-control
uninformative
no positive control; no negative control; no sensitivity or power statement		consistent-with HYPrecord
RESDoes RuF6 oxidise XeF6 to a xenon(VIII) species at RuF6:XeF6 as above, anhydrous HF, -78 degrees C?
target: xenon(VIII) fluoride species: [XeF7]+ salt or XeF8; xenon oxidation state of the isolated product = VI		condition-low-temperature-ahf
in acs-xef6-oxidation-attempts		inconclusive-no-positive-control
uninformative
no positive control; no negative control; no sensitivity or power statement		consistent-with HYPrecord
RESIs the gas evolved on mixing RuF6 and XeF6 fluorine?
target: fluorine (F2); F2 detection by KI = detected in every reaction		f2-evolved
in acs-xef6-oxidation-attempts		positive
not-applicable
rule applies to negative and inconclusive findings only		supports HYPrecord
RESWould a [XeF7][RuF6] salt be thermodynamically feasible from XeF8 and RuF5?
target: xenon(VIII) fluoride species: [XeF7]+ salt or XeF8; estimated formation energy of solid [XeF7][RuF6], solvent-corrected = -572 kJ/mol		xef7-ruf6-feasible
in acs-xef6-thermodynamics		positive
not-applicable
rule applies to negative and inconclusive findings only		supports HYPrecord
RESIs the free [XeF7]+ cation stable to loss of F2?
target: xenon(VIII) fluoride species: [XeF7]+ salt or XeF8; instability of [XeF7]+ with respect to F2 loss at 0 K (Grant et al. 2010) = 191 kJ/mol		xef7-unstable-to-f2
in acs-xef6-thermodynamics		positive
not-applicable
rule applies to negative and inconclusive findings only		supports HYPrecord
RESWhat are the fluoride ion affinities of the species involved, with and without an HF solvent model?
target: RuF6 + XeF6 reaction energetics in aHF; FIA of [XeF7]+, solvent-corrected = -379 kJ/mol		fluoride-ion-affinities
in acs-xef6-thermodynamics		positive
not-applicable
rule applies to negative and inconclusive findings only		supports HYPrecord
RESWhy does RuF6 fail to oxidise XeF6, at least under these conditions?
target: xenon(VIII) fluoride species: [XeF7]+ salt or XeF8; explanation reached = none decisive		why-it-fails
in acs-xef6-thermodynamics		partial
not-applicable
rule applies to negative and inconclusive findings only		informs HYPrecord
RESWhat is the crystal structure of the colourless product from RuF6 with excess XeF6?
target: [Xe2F11][RuF6], mu-fluorido(bis(pentafluoridoxenonium(VI)) hexafluoridoruthenate(V); R(F) for I >= 2 sigma(I) = 0.0176		crystal-structure
in acs-xef6-xe2f11-ruf6		positive
not-applicable
rule applies to negative and inconclusive findings only		supports HYPrecord
RESHow does the [Xe2F11]+ cation in the ruthenium salt compare with the Au, Sb and V salts?
target: [Xe2F11][RuF6], mu-fluorido(bis(pentafluoridoxenonium(VI)) hexafluoridoruthenate(V); Xe-F-Xe angle = 163.15 degrees		cation-geometry
in acs-xef6-xe2f11-ruf6		positive
not-applicable
rule applies to negative and inconclusive findings only		supports HYPrecord
RESDo the Raman and IR spectra of the product match the calculated spectrum of [Xe2F11][RuF6]?
target: [Xe2F11][RuF6], mu-fluorido(bis(pentafluoridoxenonium(VI)) hexafluoridoruthenate(V); agreement of observed and DFT-PBE0/TZVP band positions = good overall agreement		vibrational-spectra
in acs-xef6-xe2f11-ruf6		positive
not-applicable
rule applies to negative and inconclusive findings only		supports HYPrecord

Relations between attempts

  • acs-xef6-xe2f11-ruf6 wasDerivedFrom acs-xef6-oxidation-attempts the compound is the product of the failed oxidation with excess XeF6

Issues (5 open questions and untried branches)

  • ISS Is [XeF7]+ formed transiently and lost by F2 elimination, or never formed at all under these conditions? (open-question)
  • ISS Would a solvent other than aHF, or a different counter-anion, change the outcome, given that the salt also forms neat? (open-question)
  • ISS Find conditions under which [XeF7]+ survives long enough to be trapped as an ionic solid, since the thermodynamic estimates do not rule out [XeF7][RuF6]. (proposed-by-authors)
  • ISS Establish redox potentials or a Galvanic series for anhydrous HF. (proposed-by-authors)
  • ISS A solvent other than anhydrous HF, or a Lewis acid additive, given that aHF raises the oxidising power of F2 toward NF3 only with AsF5 or SbF5 present. (inferred-by-ingest)