High-pressure reactions of small covalent molecules. 12. Interaction of phosphorus trifluoride and sulfur hexafluoride

Hagen, A. P.; Terrell, Donald L.

doi:10.1021/ic50218a079

Cited by 8 publications

(1 citation statement)

References 6 publications

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“…SF 6 has long been regarded as an extremely inert molecule, whose few observed reactions generally occurred at high temperatures and pressures and in low yields . Only recently has it become clear that SF 6 could engage in synthetically useful reactions, specifically ones involving low-valent Ti(II) and Zr(II) organometallic complexes .…”

Section: Resultsmentioning

confidence: 99%

SF₆ as a Selective and Reactive Fluorinating Agent for Low-Valent Transition Metal Complexes

et al. 2007

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SF 6 has been found to react readily with vanadocene, yielding V(C 5 H 5 ) 2 F, while reactions with decamethylchromocene can lead to a number of products, depending on conditions. Among the products can be included Cr(C 5 Me 5 )F 2 (dmap) (dmap ) p-dimethylaminopyridine), Cr(C 5 Me 5 ) 2 + [Cr 2 (C 5 Me 5 ) 2 F 5 ] -, and Cr 8 (C 5 Me 5 ) 6 F 18 . Each of these reactions is likely to occur via the equivalent of an inner-sphere electrontransfer process. An even more rapid reaction was observed with the 19-electron Fe(C 5 H 5 )[1,3,5-C 6 H 3 -(t-C 4 H 9 ) 3 ] complex, leading to various salts of the expected 18-electron cation. In these cases, the reactions are likely to be analogous to an outer-sphere electron transfer, presumably leading initially to a "naked" fluoride ion. Structural characterization of each of these species has been obtained through X-ray diffraction studies.# Dedicated to the memory of Professor Robert W. Parry, a wonderful chemist, colleague, and human being.

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Section: Resultsmentioning

confidence: 99%

SF₆ as a Selective and Reactive Fluorinating Agent for Low-Valent Transition Metal Complexes

et al. 2007

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Fluorine Compounds, Inorganic, Phosphorus

Lindahl

Mahmood

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Phosphorus forms many fluorine compounds, including the binary fluorides, oxyfluorides, thiofluoride, and the various fluorophosphoric acids and their salts. Whereas PF 5 behaves as a Lewis acid, phosphorus trifluoride behaves as a Lewis base. PF 5 is used as a catalyst in the electronics industry and in ion implantation for semiconductors. The mono‐, di‐, and hexafluorophosphoric acids are commercially available. Hexafluorophosphoric acid is used in polymerization and preparation of its salts, a number of which exist. Particularly important commercially are sodium monofluorophosphate and potassium hexafluorophosphate, used as a dentifrice additive and as a catalyst for polymerization processes, respectively. The highly toxic fluorophosphate esters have found use in medical applications as well as in warfare. The polymerized esters are also known.

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Aktivierung von Schwefelhexafluorid an hoch reduzierten niedrig koordinierten Nickel‐Distickstoff‐Komplexen

et al. 2014

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Das Klimagas Schwefelhexafluorid ist in der Literatur ein viel verwendetes Standardbeispiel für ein sehr reaktionsträges anorganisches Molekül, das selbst durch Disauerstoff in einer elektrischen Entladung nicht angegriffen wird. Dennoch sind reduzierte b-Diketiminato-Nickel-Komplexe unter Standardbedingungen in der Lage, SF 6 in Fluorido-und Sulfido-Verbindungen zu überführen. Das Fluorido-Produkt besitzt dabei eine präzedenzlose [NiF] + -Einheit, bei der das Nickelatom nur dreifach koordiniert ist. Der Sulfido-Komplex beinhaltet eine seltene nahezu lineare [Ni(m-S)Ni] 2+ -Anordnung. Die Reaktion wurde mittels 1 H-NMR-, IR-und ESRspektroskopischen Methoden untersucht. Diese führten zur Identifizierung einer Zwischenstufe und gewährten so einen Einblick in den Mechanismus der 8-Elektronen-Reduktion von SF 6 .

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High-pressure reactions of small covalent molecules. 12. Interaction of phosphorus trifluoride and sulfur hexafluoride

Cited by 8 publications

References 6 publications

SF₆ as a Selective and Reactive Fluorinating Agent for Low-Valent Transition Metal Complexes

SF₆ as a Selective and Reactive Fluorinating Agent for Low-Valent Transition Metal Complexes

Fluorine Compounds, Inorganic, Phosphorus

Aktivierung von Schwefelhexafluorid an hoch reduzierten niedrig koordinierten Nickel‐Distickstoff‐Komplexen

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High-pressure reactions of small covalent molecules. 12. Interaction of phosphorus trifluoride and sulfur hexafluoride

Cited by 8 publications

References 6 publications

SF6 as a Selective and Reactive Fluorinating Agent for Low-Valent Transition Metal Complexes

SF6 as a Selective and Reactive Fluorinating Agent for Low-Valent Transition Metal Complexes

Fluorine Compounds, Inorganic, Phosphorus

Aktivierung von Schwefelhexafluorid an hoch reduzierten niedrig koordinierten Nickel‐Distickstoff‐Komplexen

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SF₆ as a Selective and Reactive Fluorinating Agent for Low-Valent Transition Metal Complexes

SF₆ as a Selective and Reactive Fluorinating Agent for Low-Valent Transition Metal Complexes