Intercalation of graphite by silicon tetrafluoride and fluorine to yield a second-stage salt C24SiF5

G. L. Rosenthal, T. E. Mallouk, Neil Bartlett

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Powdered graphite (either finely broken HOPG or Union Carbide SP1) interacts with 1:1 SiF4/F2 mixture (∼50 atmospheres) at 40°, to yield a second-stage compound (a0 = 2.46(1), c0 = 11.29(1) Å) of composition C∼24SiF5. This product interacts with excess PF5 with quantitative displacement of SiF4 to yield a first-stage fluorophosphate (a0 = 2.46(1); c0 = 7.65(1) A ̊) according to the equation: C24SiF5 + 2PF5 → C24PF6. PF5 + SiF4. The first-stage fluorophosphate falls to a second-stage salt (a0 = 2.46(1); c0 = 10.87 A ̊) under vacuum: C24PF6.PF5 20° → C24PF6 + PF5. This is identical to that prepared directly: 24C + PF5 + 1 2 F2 → C24PF6. Extensive reduction of C24PF6, at ≈20° : 2C24PF6 + PF3 → 48C + 3PF5 to graphite of crystallinity comparable to that of the starting graphite establishes that the initial C24SiF5 does not involve extensive fluorination of the graphite. The ease of displacement of SiF4 by superior fluoroacids indicates that C24SiF5 can be a valuable precursor for other graphite salts. Ready formation of a first-stage fluoroborate, C7BF4, Ic = 7.70(1) A ̊ contrasts with the failure to prepare similarly a first-stage SiF5- salt.

Original languageEnglish (US)
Pages (from-to)433-440
Number of pages8
JournalSynthetic Metals
Volume9
Issue number4
DOIs
StatePublished - Aug 1984

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Graphite
Fluorine
Intercalation
intercalation
fluorine
fluorophosphate
graphite
Salts
salts
Silicon
silicon
Fluorination
fluorination
carbides
Carbides
crystallinity
silicon tetrafluoride
Vacuum
atmospheres
vacuum

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Condensed Matter Physics
  • Mechanics of Materials
  • Mechanical Engineering
  • Metals and Alloys
  • Materials Chemistry

Cite this

Rosenthal, G. L. ; Mallouk, T. E. ; Bartlett, Neil. / Intercalation of graphite by silicon tetrafluoride and fluorine to yield a second-stage salt C24SiF5. In: Synthetic Metals. 1984 ; Vol. 9, No. 4. pp. 433-440.
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abstract = "Powdered graphite (either finely broken HOPG or Union Carbide SP1) interacts with 1:1 SiF4/F2 mixture (∼50 atmospheres) at 40°, to yield a second-stage compound (a0 = 2.46(1), c0 = 11.29(1) {\AA}) of composition C∼24SiF5. This product interacts with excess PF5 with quantitative displacement of SiF4 to yield a first-stage fluorophosphate (a0 = 2.46(1); c0 = 7.65(1) A ̊) according to the equation: C24SiF5 + 2PF5 → C24PF6. PF5 + SiF4. The first-stage fluorophosphate falls to a second-stage salt (a0 = 2.46(1); c0 = 10.87 A ̊) under vacuum: C24PF6.PF5 20° → C24PF6 + PF5. This is identical to that prepared directly: 24C + PF5 + 1 2 F2 → C24PF6. Extensive reduction of C24PF6, at ≈20° : 2C24PF6 + PF3 → 48C + 3PF5 to graphite of crystallinity comparable to that of the starting graphite establishes that the initial C24SiF5 does not involve extensive fluorination of the graphite. The ease of displacement of SiF4 by superior fluoroacids indicates that C24SiF5 can be a valuable precursor for other graphite salts. Ready formation of a first-stage fluoroborate, C7BF4, Ic = 7.70(1) A ̊ contrasts with the failure to prepare similarly a first-stage SiF5- salt.",
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Intercalation of graphite by silicon tetrafluoride and fluorine to yield a second-stage salt C24SiF5. / Rosenthal, G. L.; Mallouk, T. E.; Bartlett, Neil.

In: Synthetic Metals, Vol. 9, No. 4, 08.1984, p. 433-440.

Research output: Contribution to journalArticle

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T1 - Intercalation of graphite by silicon tetrafluoride and fluorine to yield a second-stage salt C24SiF5

AU - Rosenthal, G. L.

AU - Mallouk, T. E.

AU - Bartlett, Neil

PY - 1984/8

Y1 - 1984/8

N2 - Powdered graphite (either finely broken HOPG or Union Carbide SP1) interacts with 1:1 SiF4/F2 mixture (∼50 atmospheres) at 40°, to yield a second-stage compound (a0 = 2.46(1), c0 = 11.29(1) Å) of composition C∼24SiF5. This product interacts with excess PF5 with quantitative displacement of SiF4 to yield a first-stage fluorophosphate (a0 = 2.46(1); c0 = 7.65(1) A ̊) according to the equation: C24SiF5 + 2PF5 → C24PF6. PF5 + SiF4. The first-stage fluorophosphate falls to a second-stage salt (a0 = 2.46(1); c0 = 10.87 A ̊) under vacuum: C24PF6.PF5 20° → C24PF6 + PF5. This is identical to that prepared directly: 24C + PF5 + 1 2 F2 → C24PF6. Extensive reduction of C24PF6, at ≈20° : 2C24PF6 + PF3 → 48C + 3PF5 to graphite of crystallinity comparable to that of the starting graphite establishes that the initial C24SiF5 does not involve extensive fluorination of the graphite. The ease of displacement of SiF4 by superior fluoroacids indicates that C24SiF5 can be a valuable precursor for other graphite salts. Ready formation of a first-stage fluoroborate, C7BF4, Ic = 7.70(1) A ̊ contrasts with the failure to prepare similarly a first-stage SiF5- salt.

AB - Powdered graphite (either finely broken HOPG or Union Carbide SP1) interacts with 1:1 SiF4/F2 mixture (∼50 atmospheres) at 40°, to yield a second-stage compound (a0 = 2.46(1), c0 = 11.29(1) Å) of composition C∼24SiF5. This product interacts with excess PF5 with quantitative displacement of SiF4 to yield a first-stage fluorophosphate (a0 = 2.46(1); c0 = 7.65(1) A ̊) according to the equation: C24SiF5 + 2PF5 → C24PF6. PF5 + SiF4. The first-stage fluorophosphate falls to a second-stage salt (a0 = 2.46(1); c0 = 10.87 A ̊) under vacuum: C24PF6.PF5 20° → C24PF6 + PF5. This is identical to that prepared directly: 24C + PF5 + 1 2 F2 → C24PF6. Extensive reduction of C24PF6, at ≈20° : 2C24PF6 + PF3 → 48C + 3PF5 to graphite of crystallinity comparable to that of the starting graphite establishes that the initial C24SiF5 does not involve extensive fluorination of the graphite. The ease of displacement of SiF4 by superior fluoroacids indicates that C24SiF5 can be a valuable precursor for other graphite salts. Ready formation of a first-stage fluoroborate, C7BF4, Ic = 7.70(1) A ̊ contrasts with the failure to prepare similarly a first-stage SiF5- salt.

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