The preparation and characterization of radical cation salts derived from perfluorobenzene, perfluorotoluene, and perfluoronaphthalene

Richardson, T.J.; Tanzella, F.; Bartlett, Neil

doi:10.1021/ja00276a039

Cited by 64 publications

(23 citation statements)

References 3 publications

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“…This distance is remarkably short. In harmony with the use of so many of the ττ-system electrons in binding F ligands (each C to which F is bound must be an insulating Downloaded by UNIV OF ARIZONA on October 2, 2015 | http://pubs.acs.org Publication Date: May 5, 1989 | doi: 10.1021/ba-1990-0226.ch020 point in the network), C13F is an insulator. Its specific conductivity, σ ~ ΙΟ" 7 Ω" 1 cm" 1 , is attributable to F" transport in the gallery.…”

Section: Electron Affinity Valuesmentioning

confidence: 99%

Oxidative Intercalation of Graphite by Fluoroanionic Species

Bartlett

Okino

Mallouk

et al. 1989

Electron Transfer in Biology and the Solid State

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Whether oxidative intercalation of graphite by fluoroanions can occur may be estimated from the electron affinity, Ε (-ΔΗ298 in kcal mol -1 ), of the oxidizing half reaction. For first-stage salts with MF6-guests, Ε must exceed 120 kcal mol -1 . The values of E(e -+ 3 /2 MF5 --> MF6-+ 1 /2 MF3) for AsF5 and PF5 (125 and 87 kcal mol -1 , respectively) account for the spontaneous intercalation of graphite by AsF5 and the failure of PF5 to do so. Spontaneous intercalation by PF5 + F2 occurs because E(e -+ PF5 + 1 /2 F2 --> PF6-) = 165 kcal mol -1 . The thermodynamic nature of the barrier to intercalation is dem onstrated by the reduction of CxPF6 salts by PF3: CxPF6 + 1 /2PF3 --> xC + 3/2 PF5. Chlorine with certain fluoroacids can also bring about intercalation of fluoroanions. Polarizable neutral molecules, by improving the lattice energetics of graphite salts, may also be spontaneously intercalated (e.g., C14AsF6 + 1 /2AsF5 --> C14AsF 6· 1/2ASF5). When high positive charge at carbon occurs, F -is trans ferred from the fluoroanion to the carbon and novel graphite fluor ides (e.g., C1. 3F) are formed. ^flL OST OF THE REACTANTS THAT BRING ABOUT INTERCALATION of graphite are either strong oxidants or reductants such as nitric acid or alkali metal (1-3). The oxidation or reduction of the graphite that accompanies the in tercalation was clearly shown by Ubbelohde and co-workers (4-6) to be

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Section: Electron Affinity Valuesmentioning

confidence: 99%

Oxidative Intercalation of Graphite by Fluoroanionic Species

Bartlett

Okino

Mallouk

et al. 1989

Electron Transfer in Biology and the Solid State

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“…'Bartlett and co-workers (72,73) have shown that there is an essentially linear relationship, for simple A+B-salts (e.g. NaCl, KBr, KI) between the lattice energies and (molecular ~o l u m e ) "~, where the equation of the line may be represented by AU = (556.3(molecular volume)-'/' + 26.3) kcal mol-I.…”

Section: S-s'mentioning

confidence: 99%

The preparation of SeI₃SbF₆ and TeI₃SbF₆; the X-ray crystal structures of SBr₃AsF₆, SeI₃AsF₆, SeI₃SbF₆, and TeI₃SbF₆; some considerations of the energetics of the formation of SBr₃AsF₆ and SeI₃AsF₆

Johnson¹,

Murchie²,

Passmore³

et al. 1987

Can. J. Chem.

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Te13SbF6 (4) are reported and the quantitative preparation of the hitherto unknown 3 and 4 from SbF5 and the respectiye elements in SO2 are given. Crystal data are asfollows: 1, monoclinic, spacegroup P21/c, with a = 8.015(1) A, b = 9.342(1)A, c = 12.126(2), P = 97.81(1)", andZ = 4; 2, monoclinic, space group P21/c, with a = 8.380(2) 4, b = 10.237(1) 4, c = 12.524(1) A, P = 99.36(1)", and Z = 4; 3, monoclinic, space group P 2 , / c , with ci = 8.548(2) A, b = 10.297(6) A, c = 12.877(8) 6, P = 98.70(3)", and Z = 4; 4, monoclinic, space group P21/c, with a = 8.463(1) A, b = 10.676(2) A, c = 13.121(4) A, P = 100.05(1), and Z = 4.Compounds l , 2 , 3 , and 4 are isostructural and were refined to a final R values of 0.040,0.05 1,0.047, and 0.037, respectively. The structures of these salts consist of essentially discrete MX3+ cations and M1F6-anions (M = S, Se, Te; X = Br, I; M' = As, Sb) with some cation-anion interactions. The Se13+ bond distances and angles were essentially identical in both AsF6-and SbF6-salts (average Se-I distance and I-Se-I angle for AsF6-salt; 2.508(2) A, 102.4(1)" and for SbF6_ salt; 2.512(1) A, 102.3(1)"). Similarly the average Te-I bond distance and I-Te-I angle for Te13SbF6 were 2.666(1) A and 99.8(1)" which are essentially identical to those in the previously reported Te13AsF6. The average S-Br distance and Br-S-Br angle were 2.142(6) A and 103.4(2)" in SBr3AsF6. Estimates of the S-I bond distance and I-S-I bond angle in the as yet unknown S13M1F6 are made from the extrapolation of MX3+ data. The bond distances observed in the simple MX3+ cations (M = S, Se, Te; X = C1, Br, I) with anions of very low basicity are within 0.02 A of the corresponding distances calculated by the Schomaker-Stevenson equation. The observed and estimated bond distances in SBr3+, S13+, and Se13+ are significantly longer than the corresponding S-Br, S-I, and Se-I distances in S71+, S7Br+, and Se6II2+. This observation is used to support the thesis that the long intra-cationic halogen-chalcogen contacts in polychalcogen-halogen cations are weakly bonding, and responsible for the cluster-like nature of these cations. The heats of formation of 1 and 2 from their respective elements and AsF5 were estimated. On utilise cetteobservation pour supporter la thkse selon laquelle les contacts intra-ioniques halogknes-chalcog&nes, qui sont longs dans les cations polychalcogknes-halogknes, provoquent une liaisons faible qui est responsable du fait que ces cations sont pratiquement des agrkgats. On a tvaluk les chaleurs de formation des composks I et 2 h partir du AsFs et de leurs ClCments respectifs.[Traduit par la revue]

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“…[O 2 ] + is in contrast to the easy oxidation of the parent aryl compound C 6 F 6 under formation of the radical cation [C 6 F 6 ] + [24].…”

Section: [ ( S C H E M E _ 5 ) T D $ F I G ]mentioning

confidence: 99%

Explored routes to unknown polyfluoroorganyliodine hexafluorides, RFIF6

Frohn¹,

Bardin²

2010

Journal of Fluorine Chemistry

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The preparation and characterization of radical cation salts derived from perfluorobenzene, perfluorotoluene, and perfluoronaphthalene

Cited by 64 publications

References 3 publications

Oxidative Intercalation of Graphite by Fluoroanionic Species

Oxidative Intercalation of Graphite by Fluoroanionic Species

The preparation of SeI₃SbF₆ and TeI₃SbF₆; the X-ray crystal structures of SBr₃AsF₆, SeI₃AsF₆, SeI₃SbF₆, and TeI₃SbF₆; some considerations of the energetics of the formation of SBr₃AsF₆ and SeI₃AsF₆

Explored routes to unknown polyfluoroorganyliodine hexafluorides, RFIF6

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The preparation and characterization of radical cation salts derived from perfluorobenzene, perfluorotoluene, and perfluoronaphthalene

Cited by 64 publications

References 3 publications

Oxidative Intercalation of Graphite by Fluoroanionic Species

Oxidative Intercalation of Graphite by Fluoroanionic Species

The preparation of SeI3SbF6 and TeI3SbF6; the X-ray crystal structures of SBr3AsF6, SeI3AsF6, SeI3SbF6, and TeI3SbF6; some considerations of the energetics of the formation of SBr3AsF6 and SeI3AsF6

Explored routes to unknown polyfluoroorganyliodine hexafluorides, RFIF6

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The preparation of SeI₃SbF₆ and TeI₃SbF₆; the X-ray crystal structures of SBr₃AsF₆, SeI₃AsF₆, SeI₃SbF₆, and TeI₃SbF₆; some considerations of the energetics of the formation of SBr₃AsF₆ and SeI₃AsF₆