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

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

doi:10.1016/0379-6779(84)90023-7

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

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

Chemistry

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

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, I_c = 7.70(1) A ̊ contrasts with the failure to prepare similarly a first-stage SiF₅^- salt.

Original language	English (US)
Pages (from-to)	433-440
Number of pages	8
Journal	Synthetic Metals
Volume	9
Issue number	4
DOIs	https://doi.org/10.1016/0379-6779(84)90023-7
State	Published - Aug 1984

All Science Journal Classification (ASJC) codes

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

Access to Document

10.1016/0379-6779(84)90023-7

Cite this

@article{16cc6cb5da1943e1b00a30150181e150,

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

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.",

author = "Rosenthal, {G. L.} and Mallouk, {T. E.} and Neil Bartlett",

note = "Funding Information: This work was supported in part by the Committee on Research of the University of California, Berkeley, and by the Director, Chemical Sciences Division of the U.S. Department of Energy under Contract Number DE-AC03-76SF00098.",

year = "1984",

month = aug,

doi = "10.1016/0379-6779(84)90023-7",

language = "English (US)",

volume = "9",

pages = "433--440",

journal = "Synthetic Metals",

issn = "0379-6779",

publisher = "Elsevier B.V.",

number = "4",

}

TY - JOUR

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

N1 - Funding Information: This work was supported in part by the Committee on Research of the University of California, Berkeley, and by the Director, Chemical Sciences Division of the U.S. Department of Energy under Contract Number DE-AC03-76SF00098.

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.

UR - http://www.scopus.com/inward/record.url?scp=0021476828&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0021476828&partnerID=8YFLogxK

U2 - 10.1016/0379-6779(84)90023-7

DO - 10.1016/0379-6779(84)90023-7

M3 - Article

AN - SCOPUS:0021476828

SN - 0379-6779

VL - 9

SP - 433

EP - 440

JO - Synthetic Metals

JF - Synthetic Metals

IS - 4

ER -

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

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this