Neue Ringsysteme durch thermische Behandlung von (CH3NPF3)2 unter Druck

Zusammenfassung Läßt man dimeres Methyliminophosphorsäuretrifluorid einige Tage im Bombenrohr mit sich selbst reagieren, erhält man ein kristallines Produkt, das die gleiche Zusammensetzung wie das flüssige Ausgangsprodukt hat. Daraus läßt sich durch Extraktion mit CCl₄ ein Tetrameres, (CH₃NPF₃)₄, gewinnen; der Rückstand ist die ionisch aufgebaute Verbindung (CH₃N)₄P₃F₆ ⁺PF₆ ^–. Aus letzterer erhält man durch Vakuum-sublimation in guter Ausbeute unter Verlust von PF₅ die Verbindung (CH₃N)₄P₃F₇.

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Alkylimino phosphoric acid trihalides, II: New ring systems by heating(CH ₃ NPF ₃)₂ in a sealed tube

Prolonged heating (several days) of (CH₃NPF₃)₂ in a sealed tube yields a crystalline product having the same composition as the liquid starting material. By CCl₄-extraction of this material the tetrameric compound (CH₃NPF₃)₄ can be isolated. The residue is the ionic compound (CH₃N)₄P₃F₆ ⁺PF₆ ^–. Vacuum sublimation of this product yields (CH₃N)₄P₃F₇.

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Mit 3 Abbildungen     

Fluordiazadiphosphetidine, 17. Mitt.

The reactions of (CH₃NPF₃)₂ and F₃P(CH₃N)₂PF₂OCH₃ with lithium-1,1,1-trimethyl-N-(trimethylsilyl)-silanamide yield two new dispiro-compounds:XF₂P(CH₃N)₂PF(NSiCH₃)₂PF(CH₃N)₂PF₂ X withX=F, OCH₃. Synthesis, mass-spectra and X-ray structures are discussed.

Herrn Prof. Dr.K. L. Komarek zum 60. Geburtstag gewidmet.     

Reaction of PF5·CH3CN with sulfide

Nitriles react with PF₅ and also with AsF₅, SbF₅ forming 1:1-adducts. Using C₂Cl₃F₃ as a solvent is of advantage for this reaction. PF₅·CH₃CN and [N(C₂H₅)₄]SH give [N(C₂H₅)₄][P₂S₂F₈] with a sulfur double bridge and hexafluorophosphate in acetonitrile [1]. In case of AsF₅·CH₃CN a salt with the anion [AsF₅NHCSCH₃]^? has been isolated [2]. Following products have been confirmed in a reaction mixture of PF₅·CH₃CN and SH^? in acetonitrile by NMR (³¹P and ¹⁹F): [PF₆]^?, [F₅PSPF₅]^2?,

, F₄PSH, F₃PS, HPS₂F₂, [PS₂F₂]^?, [F₅PNC(SH)CH₃]^?, [F₅PNHCSCH₃]^?, [F₅PSH]^?. With a ratio PF₅·CH₃CN: SH^? = 2:1 the S-bridge-complexes are prefered whereas in case of a ratio 1:1 the non-bridged P-complexes are the main products.     

Fluordiazadiphosphetidine, 3. Mitt.: Die thermische Behandlung von 2,2,2,4,4,4-Hexafluoro-1,3-dimethyl-1,3,2,4-diazadiphosphetidin unter Druck in Gegenwart von Phosphor(V)fluorid und Alkalimetallfluoriden

Prolonged heating of (CH₃NPF₃)₂ in a sealed tube at 120°C yields (CH₃N)₄P₃F₇ and PF₅. Under the experimental conditions these compounds react to (CH₃N)₄P₃F₆ ⁺PF₆ ^–. Reaction of (CH₃NPF₃)₂ in the presence of PF₅ leads to a marked decrease in the formation of the ionic compound. The influence of the fluoride donating saltsMF (M=Li, Na, K, Cs) is investigated.

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Mit 1 Abbildung

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Früher: Alkyliminophosphorsäuretrihalogenide, 1. und 2. Mitt.     

Fluordiazadiphosphetidine, 20. Mitt. Die Dehydrofluorierung zwitterionischer und die Hydrofluorierung neutraler,hydrazinsubstituierter Fluordiazadiphosphetidine

In the presence ofEt ₃N·PF₅, F₄P^–(CH₃N)₂PF₂NHNH⁺(CH₃)₂ (I) looses one molecule of HF to yield F₃P(CH₃N)₂PF₂NHN(CH₃)₂ (II). The reaction ofI withDABCO (1,4-diazabicyclo[2.2.2]octane) yieldsDABCO·2H⁺⁺(CH₃NPF₄) ₂ ^–– (III) and [CH₃NPF₂NHN(CH₃)₂]₂ (IV). Even in the presence of CsF,II does not react with HF.

     

Gasphasenreaktionen von H3PF2: Darstellung der Monohalogenphosphane H2PF und H2PCl

Gas Phase Reactions of H₃PF₂: Synthesis of the Monohalogenophosphanes H₂PF and H₂PCl Gas phase reactions of H₃PF₂ at ≤ 10 mbar with hydrides (B₂H₆, HSi(CH₃)₃, HSn(CH₃)₃), amines (H₃N, N(CH₃)₃) and electrophilic halides of B, Si and Ti in the beam of an IR interferometer have been investigated with a time delay of 15 sec. between successive measurements. Gas/solid phase reactions of H₃PF₂ with KF and AlCl₃ and reactions of H₃PF₃ and HPF₄ have been studied similarly. With H₃N, N(CH₃)₃ and electrophilic halides, H₃PF₂ was converted into its dehydrofluorination product H₂PF. This eliminates further HF in the presence of H₃N or N(CH₃)₃, while BCl₃ or TiCl₄ yield the hitherto unknown H₂PCl. The IR spectra of the short-lived species H₂PF and H₂PCl as well as their deuterated isotopomers, which reveal at room temperature and ≤ 10 mbar a halflife time of ≤ 12 min. and ≤ 50 sec. respectively, were recorded and analysed in order to characterize the novel species.     

Metal complexes of fluorophosphines : III. Some oxidative addition reactions of a rhodiumtrifluorophosphine complex

Some oxidative addition reactions of (CH₃)₅C₅Rh(PF₃)₂ with various iodine compounds are described. Iodine reacts with (CH₃)₅C₅Rh(PF₃)₂ in benzene at room temperature to give the deep red crystalline diiodide (CH₃)₅C₅Rh(PF₃)I₂. The perfluoroalkyl iodides R_fI (R_f = CF₃, C₂F₅, n-C₃F₇, and n-C₇F₁₅) react with (CH₃)₅C₅Rh(PF₃)₂ in benzene at room temperature to give the orange to deep red (CH₃)₅C₅Rh(PF₃)(R_f)I (R_f = CF₃, C₂F₅, n-C₃F₇, and n-C₇F_l5). The IR and proton and fluorine NMR spectra of these new (pentamethylcyclopentadienyl)rhodium-trifluorophosphine complexes are discussed.     

Effects on Coordination of Thioether Sites. 4. Structural Analysis of η3-Tripodal Ligand Manganese(I) Complexes

Crystal structures of a series of manganese(I) complexes containing tripodal ligands were determined. For [η³-{CH₃C(CH₂PPh₂)₂(CH₂SPh)-P,P′,S}Mn(CO)₃]PF₆ ( 1 ): a = 10.856(3) Å, b = 19.698(3) Å, c = 17.596(5) Å, β = 96.17(2)°, monoclinic, Z = 4, P2₁/c, R(F_o) = 0.068, R_w(F_o) = 0.055 for 3617 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)(CH₂SPh)₂-P,P′,S}Mn(CO)₃]PF₆ ( 2 ): a = 9.890(2) Å, b = 20.403(4) Å, c = 10.269(3) Å, β = 117.44(2)°, monoclinic, Z = 2, P2_l, R(F_o) = 0.050, R_w(F_o) = 0.037 for 1760 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)₂(CH₂S)-P,P′,S}Mn(CO)₃] ( 4 ): a = 8.191(7) Å, b = 10.495(3) Å, c = 19.858(6) Å, α = 99.61(2)°, β = 96.17(2)°, γ = 92.70(4)°, triclinic, Z = 2, P-I, R(F_o) = 0.048, R_w(F_o) = 0.039 for 2973 reflections with I_o > 2σ(I_o). There is no significant difference in the bond lengths of Mn-S bonds among three species in their crystal structures [2.325(2) Å in 1; 2.358(4) in 2; 2.380(2) in 4], but the better donating ability of thiolate in complex 4 appears on the lower frequencies of its carbonyl stretching absorptions.     

Fluorierte Elementorganica: Oxidative Flüssigphasen-Direktfluorierung. X. Organyloxyfluorphosphorane: Direktsynthese durch F2-Addition an Phosphinic-, Phosphonic- sowie Phosphoricsäureester(fluoride) und Thermolyseverhalten

Fluorinated Organoelements: Oxidative Liquid-Phase Direct Fluorination. X. Organyloxyfluorophosphoranes: Direct Synthesis by F₂-Addition to Phosphinic-, Phosphonic-, and Phosphoric-Acid Ester(fluorides) and Thermal Behaviour The phenoxyfluorophosphoranes (PhO)₂PF₂R ( 2a: R = CH₃, 2b: R = Ph) and (PhO)_3?nPF_n+2 ( 4a: n = 0, 4b: n = 1, 4c: n = 2) were obtained in reasonable yield by direct fluorination of the corresponding organyloxy(fluoro)phosphanes for the first time. Contrary to 4c the intramolecular ligand exchange can be frozen up in 4b. The up to now unknown thermally unstable alkoxy-substituted difluorides (AlkO)_3?PF₂R_n ( 6a: Alk = CH₃, R = Ph), n = 2; 6b: Alk = CH₂CF₃, R = Ph, n = 2; 6c: Alk = CH₃, R = Ph, n = 1; 6d: Alk = CH₃, n = 0) were isolated by low temperature F₂-addition in pure substance, too. Their thermal decomposition (scrambling, CH₃F-elimination) was cleared up for 6a as model substance and transferred to (CH₃O)₃PF₂ 6d Here the splitting of (CH₃)₂O under “Arbusov-conditions” is very surprising. The trigonal bipyramidal covalent structure of all organyloxyphosphoranes was confirmed by multinuclear ¹⁹F, ³¹P{¹H}, ¹³C{¹H}) NMR experiments.     

Reactions of coordinated trimethylphosphite with binary fluorides

Fluorination of free trimethylphosphite by phosphorus pentafluoride or tungsten hexafluoride involves complex formation followed by rapid F-for-OCH₃ exchange and Michaelis-Arbusov rearrangement reactions (D.W.A. Sharp et al., $\text{J. Chem. Soc. A}$, 1969, 872; J.M. Winfield et al., $\text{ibid}$, 1970, 501). Reactions between WF₆ or PF₅ and P(OCH₃)₃, coordinated to Fe^II (low spin d⁶-inert) or Cu^I (d¹⁰ -labile) cations in CH₃CN, counter anions PF₆^? or AsF₆^?, are very different as evidenced by an n.m.r. study.Reactions between Fe^IIP(OCH₃)₃ and WF₆ are very slow at room temperature; the major products are CH₃PF₄ and WOF₄.NCCH₃. Reactions between Cu^IP(OCH₃)₃ and WF₆ or PF₅ are rapid, even below room temperature, and depend on the stoicheiometry. The major products are W₂O₂F₉^? and a PF₅X^? species, or OPF₃, minor products include CH₃OPF₂, (CH₃O)₂PF, and PF₃. When the mole ratio coordinated P(OCH₃)₃:WF₆ is 1:1, additional W₂O₂F₉ and PF₅X n.m.r. signals are observed.The reactions involve fluorination of free P(OCH₃)₃ whose concentration in solution is limited by the metal cation, and in the reaction between PF₅ and Cu^IP(OCH₃)₃ PF₅.P(OCH₃)₃ has been identified as the initial product. Conventional Michaelis-Arbusov rearrangements are of minor importance as CH₃CN acts as a sink for CH₃⁺, but the final step in the formation of CH₃PF₄ is of this type.     

[t-Bu2P]3P7 und (t-Bu2Sb)3P7 sowie Untersuchungen zur Bildung von Heptaphosphanen(3) mit PMe2-, PF2- und P(CF3)2-Gruppen

[t-Bu₂P]₃P₇ and (t-Bu₂Sb)₃P₇, as well as Investigations on the Formation of Heptaphosphanes (3) Containing PMe₂, PF₂, and P(CF₃)₂ Groups Tris(di-tert-butylphospha)heptaphosphanortricyclane (t-Bu₂P)₃P₇ 1 obtained by reacting Li₃P₇ · 3 DME with t-Bu₂PF forms yellow crystals. (t-Bu₂Sb)₃P₇ 2 produced similarly from t-Bu₂SbCl and Li₃P₇ · 3 DME didn't form crystals; it decomposes in a solution of toluene above ?10°C. Both compounds were identified by their ³¹P{¹H} NMR spectra, and 1 also by elemental analysis and single crystal structure determination (space group) P2₁/a, a = 1 712.0(9) pm, b = 1 105.1(7) pm, c = 1 854.0(10) pm, β = 94.96(4)°, Z = 4 formula units in the elementary cell). Attempts to synthesize (Me₂P)₃P₇ 3 , (F₂P)₃P₇ 4 and [(F₃C)₂P]₃P₇ 5 failed as dialkylchlorophosphanes as Me₂PCl e. g. with Li₃P₇ · 3 DME react under Li/Cl exchange, dialkylfluorophosphanes (except t-Bu₂PF) disproportionate, and neither PF₃ nor (F₃C)₂PBr with Li₃P₇ · 3 DME give the desired products 4 or 5 , resp.     

Die Reaktion der Zweikomponentensysteme P(OR)3 − x(NR2)x (x = 0–3)/CCl4 und P4/CCl4 mit HF-Donatoren

Reaction of the Two-component Systems P(OR)_{3 ? x}(NR₂)_x (x = 0–3)/CCl₄ and P₄/CCl₄ with HF-Donators The combination of organylammonium fluorides and carbon tetrachloride is a good agent for oxidative fluorination of trivalent phosphorus compounds. As oxidation products [(RO)PF₅]^? and (RO)₂P(O)F are obtained from P(OR)₃, (Et₂N)₂P(O)F and (Et₂N)₂(EtO)PF₂ from P(OEt)(NEt₂)₂ as well as (Et₂N)₃PF₂ and [(Et₂N)₃PF]⁺ from P(NEt₂)₃. In the system R₂NH/CCl₄/Et₃N · n HF P₄ is fast oxidized forming [HPF₅]^?, R₂NH · PF₅ and (R₂N)₂P(O)F. In the case of simultaneous addition of alcohols [(RO)PF₅]^?, (RO)₃PO and (R₂N)₂P(O)F are formed. The reactions are controlled by the nucleophilic power and the concentration of fluoride, the acidity of the system, and the temperature.     

Fluordiazadiphosphetidine, 4. Mitt. Die thermische Behandlung von (CH3N)4P3F7

(CH₃N)₄P₃F₇ decomposes at 130 °C in a closed system yielding 2,2,2,4,4,4-hexafluoro-1,3-dimethyl-1,3,2,4-diazadiphosphetidine (CH₃NPF₃)₂, an anionic compound, and the new highly condensed ring system (CH₃N)₆P₄F₈.

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Früher: Alkyliminophosphoräuretrihalogenide 1. und 2. Mitteilung.     

Methandiphosphor-Halogen-Verbindungen

Methylene-diphosphorus Halides The synthesis of methylene-bridged diphosphorus halides of the type X₂P(Z)CH₂PX₂, X₂P(Z)CH₂P(Z)X₂ and F₄PCH₂P(Z)X₂(with X = F, Cl; Z = O, S) as well as the preparation of the fluorophosphorane F₄PCH₂PF₄, and of the two anions, [F₅PCH₂PF₅]^2? and [F₅PCH₂P(O)F₂]^?, is reported.     

Chemistry in fuming nitric acids—I. NMR spectroscopic study of PF5, HPO2F2 and P4O10 in the solvent system 44 wt.% N2O4 in 100% HNO3

³¹P and ¹⁹F NMR spectroscopy has been used to elucidate the nature of the interaction of PF₅, HPO₂F₂ and P₄O₁₀ with the solvent system 44 wt.% N₂O₄ in 100% HNO₃ (“High Density Acid”, HDA). PF₅ generates the species PF₆^?, HPO₂F₂ and HF (with some H₂PO₃F present as a minor product). HPO₂F₂ gives rise to H₂PO₃F and HF (with smaller amounts of PF₆ also present). The ³¹P NMR spectrum of P₄O₁₀ in HDA exhibits four resonances assigned to P(OH)₄⁺, H₄P₂O₇, (HPO₃)₄ and a mixture of cyclic and branched phosphoric acids, respectively.     

Hydrofluorierung von Bis(silylimido)tetramethyldiphosphoran

Hydrofluorination of Bis(silylimido)tetramethyldiphosphorane The silylated bis(imidophosphorane), (CH₃)₂P[NSi(CH₃)₃]? P[NSi(CH₃)₃](CH₃)₂, 1 reacts in ether with hydrogen fluoride to give the tetrafluorodiphosphorane, (CH₃)₂PF₂? PF₂(CH₃)₂, 2 , while hydrofluorination in fluorotrichloromethane gives the diazadiphosphetidin 3 and the iminophosphorane 4 . The thermal decomposition of 2 , studied by ¹⁹F and ³¹P-n.m.r. spectroscopy, yields trifluorodimethylphosphorane and tetramethyldiphosphane.     

Fluordiazadiphosphetidine, 6. Mitt.Die reaktion von 2,2,2,4,4,4-Hexafluoro-1,3-dimethyl-1,3,2λ5,4λ5-diazadiphosphetidin mit Fluorwasserstoff

Reaction of (CH₃NPF₃)₂ with dry hydrogen fluoride yields CH₃NH₃+PF₆-and the new compound (CH₃NHPF₄)₂.

     

Über die Kristallstrukturen von CH3PF2H+AsF6− und CH3PF2H+SbF6− und eine einfache Darstellung von CH3PF2

On the Crystal Structures of CH₃PF₂H⁺AsF₆^? and CH₃PF₂H⁺SbF₆^? and a simple Method for Preparation of CH₃PF₂ A simple method for preparation of CH₃PF₂ from CH₃PCl₂ is reported. The phosphonium salts CH₃PF₂H⁺MF₆^? are obtained by the reaction of CH₃PCl₂ with superacidic systems HF/MF₅ (M = As, Sb). CH₃PF₂H⁺SbF₆^? crystallizes in the space group P1 with a = 548.4(4) pm, b = 695.5(8) pm, c = 960.2(9) pm, α = 94.68(5)°, β = 97.19(6)°, γ = 94.41(6)° and Z = 2. CH₃PF₂H⁺SbF₆^? crystallizes in P1 with a = 554.3(3), b = 724.2(4), c = 970.4(5), α = 94.73(4)°, β = 96.14(5)°, γ = 95.30(4)°.     

Struktur und Eigenschaften von Methyltrifluorphosphoran CH3PF3H

Structure and Properties of Methyltrifluorophosphorane CH₃PHF3₃ Methyldichlorophosphane reacts with three equivalents of HF under formation of Methyltrifluorophosphorane, which is characterized by mass, NMR, and vibrational spectroscopy. The ab intio calculation (HF/6‐31+G*) yields a distorted trigonal bipyramidal structure for CH₃PF₃H. The methyl group (r P—C = 180.2 pm), the hydrogen (r P—H = 137.1 pm) and one fluorine atom (r P—F_eq = 155.8 pm) are located at equatorial positions. The P—F_ax‐distance is 163.4 pm. The Lewis‐amphoteric properties are shown by reactions with CsF, [(CH₃)₄]NF and AsF₅.     

Synthese von Fluoro-λ5-monophosphazenen und Fluoro-1, 3-diaza-2λ5, 4λ5-diphosphetidinen mittels der Staudinger-Reaktion

Synthesis of Fluoro-λ⁵-monophosphazenes and Fluoro-1,3-diaza-2λ⁵,4λ⁵-diphosphetidines by Means of the Staudinger Reaction 35 Tetrafluoro- and 2 difluorodiaza-diphosphetidines as well as 4 difluoro- and 30 monofluoro-λ⁵-monophosphazenes were prepared by the Staudinger reaction between tervalent phosphorus fluorides, R_nPF_3?n (n = 1, 2; R = R₂N, (CH₂)₅N, O(CH₂)₄N, RO, (CH₂O)₂, alkyl, aryl) and phenylazides, X? C₆H₄N₃ (X = H, 4-CH₃, 4-Cl, 4-Br, 4-NO₂, 3-NO₂). PF₃ does not react with phenylazide The influence of substituents on the structure of the reaction products is discussed. Kinetic measurements allowed to determine the constants λ^P_I of the substituents (CH₂)₅N, O(CH₂)₄N and R(C₆H₅)N (R = CH₃, C₂H₅, n-C₄H₉).