Reaktionen des Trichlorphosphazophosphordichlorids,Cl3PN?PCl2

Reactions of Trichlorophosphazophosphorusdichloride, Cl₃P?N? PCl₂ P₂NCl₅ reacts with SbF₃ to give P₂NCl₃F₂ from which P₂NCl₄F is obtained by chlorination. Sulfur oxidizes P₂NCl₅ to yield SP₂NCl₅, SO₂ to yield SP₂NCl₅ and OP₂NCl₅. Reaction product from P₂NCl₅ and H₂S is SPCl₂(NH₂) besides PCl₃. P₂NCl₅ reacts with (n-C₄H₉)₃P to give (n-C₄H₉)₃P?N? PCl₂. All new compounds are characterized by their n.m.r. spectra and their chemical behaviour.     

Über Phosphorstickstoff-Verbindungen XXVIII. Über Reaktionen von Cyanamid,Dicyanimid und Dicyandiamid mit PCl5

Interaction between cyanamide and PCl₅ in the mole ratio 1:3 yields the phosphazenium salt [Cl₃P?N? C(Cl)?N? PCl₃] [PCl₆]. The reaction of sodium dicyanimide and PCl₅ gives 1. 1. 3. 5-tetrachloro-1-phospha-2. 4. 6-triazine (compound B in ?Inhaltsübersicht”?). Dicyandiamide and PCl₅ (1:2) give compound C and, at milder conditions the salt-like phosphatriazine D. Solvolysis of C with formic acid or of D with sulphur dioxide yields E.     

Oligomere μ-Imidophosphorsäurechloride und -amide

Oligomeric μ-Imidophosphoric Acid Chlorides and Amides Oligomeric μ-imidophosphoric acid chlorides. Cl₂(O)P? [NH? P(O)Cl]_n? Cl, (n = 1, 2, 3) are obtained by solvolysis of the linear phosphorylchlorphosphazenes, Cl₂(O)P? [N?PCl₂]_n? Cl, with the stoichiometric amount of anhydrous formic acid. The chlorides react with ammonia forming the amides. The amides are characterized by paper and gel chromatography. Course and rate of hydrolysis of diimidotriphosphoric acid pentaamide depend on pH.     

Synthese und Eigenschaften linearer Phosphorylchlorphosphazene

Synthesis and Properties of Lineary Phosphorylchlorphosphazenes The phosphorylchlorphosphazenes, Cl₂(O)P—[N?PCl₂]_n—Cl, (n = 1, 2, 3) react like POCl₃ with hexamethyldisilazan forming silylamides, Cl₂(O)P—[N ? PCl₂]_n—NHSi(CH₃)₃, (n = 0, 1, 2, 3). From these are obtained the phosphorylchlorphosphazenes by reaction with PCl₅ containing one group —N ? PCl₂ more.     

Zur Kenntnis der Chemie der Silazane. IV. Über ein Sulfurylphosphazo-silazan

Trichlorophosphazo-sulphurylchloride. Cl₃P?N? SO₂Cl, reacts with heptamethyldisilazane to yield the Si? N? P compound (I) formulated in ?Inhaltsübersicht”?. (I) reacts with PCl₅ or C₆H₅? PCl₄ forming the known 2,2,2,4,4,4-hexachloro-1,3-di-methylcyclo-diphosphazane(II), accompanied by the compound Cl₃P?N? SO₂Cl and C₆H₅? PCl₂?N? SO₂Cl, respectively, which were detected by means of ³¹P-NMR spectroscopy.     

Über Trichlorphosphazo-Verbindungen aus Nitrilen. III. Die Reaktion zwischen Acrylnitril und PCl3

On Trichlorophosphazo Compounds from Nitriles. III. The Reaction between Acrylonitrile and PCl₃. The reaction of PCl₃ with acrylonitrile at higher temperatures gives CH₂Cl? CCl₂? CCl₂? N? PCl₃ ( II ). On pyrolysis of (II), CH₂Cl? CCl₂? CN (IV) is form- ed. Treatment of (II) with SO, results in CHzCL? CCl₂? CCl?N-P(0)Cl₂ ( III ). At lower temperatures and/or in the presence of PCl₃, acrylonitrile reacts with PCl₃ to give the cis/ trans isomers VIa and VIb .     

Zur Kenntnis des Aluminiumchlorids. Die Umsetzung von AlCl3 mit PCl5 und Methylamin

Aluminium trichloride forms the adducts AlCl₃ · NH₂CH₃, AlCl₃ · 2NH₂CH₃, AlCl₃ · 4NH₂CH₃; AlCl₃ · NH₃CH₃Cl, AlCl₃ · 2NH₃CH₃Cl. The interaction between AlCl₃, PCl₅ and NH₃CH₃Cl in the molar ratio 1:3:2 proceeds according to the reaction equation in “Inhaltsübersicht”. On applying other stoichiometric amounts, [Cl₂(NHCH₃)P? N(CH₃)? AlCl₃] · HCl and [Cl₃P? N(CH₃)? AlCl₃] · HCl are obtained; the latter reacts as [Cl₃P? NHCH₃][AlCl₄]. At the molar ratio AlCl₃:PCl₅:NH₃CH₃Cl = 1:2:4 a compound is formed being presumably the six-membered heterocycle formulated in “Inhaltsübersicht”. With [Cl₃P?N? PCl₃] and aluminium chloride [Cl₃P?N? PCl₃][AlCl₄] is formed.     

Kristallstruktur und Schwingungsspektrum von Tris-trichlorophosphazeno-carbenium-hexachloroantimont [C(N  PCl3)3]+SbCl6−

Crystal Structure and Vibrational Spectrum of Tris-trichlorophosphazeno-carbenium-hexachloroantimonate [C(N?PCl₃)₃]⁺SbCl₆^? [C(N?PCl₃)₃]SbCl₆ crystallizes in the space group P1 with the lattice constants a = 903 b = 1046, c = 1307 pm and α = 94.8, β = 88.3, γ = 103.8°. Using X- ray diffraction data, the crystal structure was determined and refined to a residual index of 0.027. The structure consists of octahedral SbCl₆^? ions and [C(N?PCl₃)₃]⁺ ions having approximately C_3h symmetry; the atoms C, N, P, and one Cl per PCl₃ group lie approximately in a plane. The i. R. and Raman spectrum was registered and assigned.     

Darstellung und Schwingungsspektren von Verbindungen des Typus X3PNCH3

Preparation and Vibration Spectra from Compounds of the Type X₃PNCH₃ Preparation, qualities, and vibration spectra of [F₃PNCH₃]₂, [Cl₃PNCH₃]₂, (MeO)₃PNMe, (Me₂N)₃PNMe and P(NMe₂)J^? are reported. An assignement to the normal vibrations is tried. Finally the frequencies of the different P? N bonds are discussed.     

Fluoridolyse von N-Phosphorylphosphazenen

Fluoridolysis of N-Phosphoryl Phosphazenes In the reaction of the N-phosphoryl phosphazenes X₃P?N? P(Y)X₂ (X = Cl, PhO, Et₂N, CF₃CH₂O, PrS, Ph; Y = O, S) ( 1 – 18 ) with Et₃N · nHF (n ≈? 3 or 0.6) fluoro derivatives of N-phosphoryl phosphazenes (see table 2) as well as N-phosphorylated imiddotetrafluorophosphates, [F₄P?N? P(Y)Cl₂]^? (Y = O, S), and imidopentafluorophosphates, [F₅P? N? P(Y)X₂]^2? or [F₅P? NH? P(O)X₂]^? (see table 3), are formed. t-BuNHPCl₂?N? POCl₂ reacts in acetonitrile with Et₃N or i-Pr₂EtN to form a product, representing probably the diazadiphosphetine ( 5 b ).     

Additions- und SubstitutionsReaktionen an Tetrafluor- und Tetrachlordiboran(4)

Addition and Substitution Reactions at Tetrafluoro- and Tetrachlorodiborane(4) From equimolar mixtures of B₂F₄ and Me_nN(SiMe₃)_3-n (n = 0–3) the mono-addition products 1–4 are formed at low temperatures. By elimination of Me₃SiF the adduct 2 gives the dimeric monosubstituted diborane 8 , which slowly decomposes at room temperature to the aminoborane 6 and (BF)_n. The course of the reactions was studied by means of ¹¹B and ¹⁹F NMR spectroscopy and by measuring the vapor pressures. According to the ¹¹B and ³¹P NMR spectra the reaction of B₂Cl₄ with PCl₅ or [Me₄N]Cl in liquid hydrogen chloride at 0°C does not yield [PCl₄]₂⁺[B₂Cl₆]^2? or [Me₄N]₂⁺[B₂Cl₆]^2? but gives [PCl₄]⁺[BCl₄]^?, PCl₃ and BCl₃ or [Me₄N]⁺[BCl₄]^? and BCl₃ besides (BCl)_n.     

Synthese linearer und verzweigter Phosphazene aus N-silylierten Phosphorylamiden

Synthesis of Lineary and Branched Phosphazenes from N-silylated Phosphoryl Amides The use of N-silylated phosphoryl amides in the reaction with PCl₅ favours the KIRSANOV reaction and reduces undesirable substitution reactions. However, silylated monoamides, X₂P(O)NHSiMe₃ (X = OEt, NEt₂), do not give the expected trichlorophosphazenes but the isomeric N-dichlorophosphoryl phosphazenes, Cl₂P(O)? N?PClX₂, which are also formed in the reaction of (EtO)₂P(O)NCl₂ with PCl₅. As the first phosphoryl-P, P-bis(trichlorophosphazene) (EtO)P(O)(N?PCl₃)₂ could be obtained in the reaction of PCl₅ with the silylated diamide (EtO)P(O)(NHSiMe₃)₂. Tris reactivity of silylated amides to P? Cl compounds decreases in the row PCl₅ > POCl₃ > CIP(O)(OEt)₂ > ClP(O)(NEt₂)₂. In the reaction with phosphoryl chlorides the preferred formation of compounds with P? NH? P bridges could not be observed.     

NH4[Re3Cl10(OH2)2] · 2 H2O: Synthese und Struktur Ein Beispiel für starke N?H …︁ O- und O?H …︁ Cl-Bindungen

NH₄[Re₃Cl₁₀(OH₂)₂] · 2 H₂O: Synthesis and Structure. An Example for “Strong” N? H …? O and O? H …? Cl Hydrogen Bonding The red NH₄[Re₃Cl₁₀(OH₂)₂] · 2 H₂O crystallizes from hydrochloric-acid solutions of ReCl₃ with NH₄Cl. It is tetragonal, P4₁2₁2, No. 92, a = 1157.6, c = 1614.5 pm, Z = 4. The crystal structure contains “isolated” clusters [Re₃Cl₁₀(OH₂)₂]^?. These contain Cl…?H? O? H…?Cl units with “very strong” hydrogen bonds: distances Cl? O are only 286 pm. NH₄⁺ has seven Cl^? as nearest neighbours and, additionally, one H₂O which belongs to a cluster [d(N? O1) = 271 pm] and one crystal water [d(N? O2) = 286 pm].     

Nitrosyl-tetrachloro-dichlorphosphato-molybdat(+II); Darstellung,IR-Spektrum und Kristallstruktur von (AsPh4)2[Mo(NO)Cl4(O2PCl2)]

Nitrosyl-tetrachloro-dichlorophosphate-molybdate(+II); Preparation, I.R. Spectrum and Crystal Structure of (AsPh₄)₂[Mo(NO)Cl₄(O₂PCl₂)] The title compound is prepared by the reaction of AsPh₄[Mo(NO)Cl₄] with AsPh₄? [PO₂Cl₂] in dichloromethane solution. It forms orange crystals which are only little sensitive to moisture. The complex crystallizes triclinic in the space group P1 with two formula units in the unit cell. The structure was solved by X-ray diffraction methods (2498 observed, independent reflexions, R = 5.4%). The compound consists of AsPh₄^⊕ cations and [Mo(NO)Cl₄(PO₂Cl₂)]^2? anions. The NO ligand is coordinated in linear array \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {{\rm MO}}\limits^ \ominus = \mathop {\rm N}\limits^ \oplus = {\rm O}(177^{\circ}) $\end{document}. The dichlorophosphate group is coordinated in trans position to the NO ligand with one of its oxygen atoms. The Mo?N bonding of the NO ligand causes the bond angle NMoCl of 93.2° in average. The IR spectrum is recorded and assigned.     

Reaktionen von Phosphorigsäure-bis(dimethylamid) und Phosphorsaäure-tris(methylamid) mit PCI3

Reactions of Phosphorous Bis(dimethylamide) and Phosphoric Tris(methylamide) with PCI₃ From the products of the reaction between phosphorous bis(dimethylamide) and PCl₃ in the presence of pyridine the pentakis(dimethylamide) of acid can be isolated. The reaction between phosphoric tris(methylamide) and PCl₃ in the presence of pyridine yields crystalline O = P[NCH³? PCl₂]₃ which can be converted into O = P[NCH³? PF₂]₃ with SbF₃ or AsF₃. The nmr data of the new compounds and some by-products of the reaction are given and discussed.     

Über die Gasphasenstruktur von CF3NCl2 und die Darstellung von CF3NCl2F+MF6− (M = As,Sb) und CF2 = NClF+SbF6−

Gas Phase Structure of CF₃NCl₂ and Preparation of CF₃NCl₂F⁺MF₆^? (M = As, Sb) and CF₂ = NCl₂F⁺SbF₆^? The gas phase structure of CF₃NCl₂ is reported. The following skeletal parameters are derived (r_a-values, error limits are 3σ values): N? C = 1.470(6) Å, N? Cl = 1.733(3) Å, ClNCl = 111.5(4)° and ClNC = 107.6(5)°. CF₃NCl₂F⁺MF₆^? is prepared by fluorination of CF₃NCl₂ with XeF⁺MF₆^?. The same educt CF₃NCl₂ reacts with XeF⁺SbF₆^? at ?40°C to CF₂ = NClF⁺SbF₆^? under elimination of ClF.     

Umsetzungen von Ferrocenol und 1,1′-Ferrocendiol mit Cyclotriphosphazenen,P3N3F6 und P3N3Cl6

Reactions of Ferrocenol and 1,1′-Ferrocendiol with Cyclotriphosphazenes, P₃N₃F₆ and P₃N₃Cl₆ The hexahalogeno-cyclotriphosphazenes, P₃N₃X₆ (X ? F ( 1 a ), Cl ( 1 b )), react with ferrocenol (FcOH) in a molar ratio 1 : 1 to give the ferrocenoxy derivatives, FcO[P₃N₃X₅] (X ? F ( 3 a ), Cl ( 3 b )); in an analogous manner the tetrameric ring P₄N₄Cl₈ ( 2 b ) is converted to FcO[P₄N₄Cl₇] ( 4 b ).

1 Abkürzungen: Fc = Ferrocenyl, (C₅H₅)Fe(C₅H_4?); fc = 1,1′-ferrocendiyl, Fe(C₅H_4?)₂; rc = 1,1′-ruthenocendiyl, Ru(C₅H_4?)₂. Fluorphosphazene werden mit a , Chlorphosphazene mit b gekennzeichnet.

With 1,1′-ferrocenediol, (fc(OH) ₂ ), the cyclo triphosphazenes react in a molar ratio 1 : 1 to produce fcO ₂ [P ₃ N ₃ X ₄ ] (X ? F ( 5 a ), Cl ( 5 b )). According to the x-ray structure analysis, the 1,1′-ferrocenediolato group in 5 a , b is bound to two different phosphorus atoms. On the contrary, the 1,1′-ferrocenedithiolato- and 1,1′-ferrocenediselenolato units in fcS ₂ [P ₃ N ₃ X ₅ ] (X ? F ( 6 a ), Cl ( 6 b )) and fcSe ₂ [P ₃ N ₃ X ₅ ] (X ? F ( 7 a ), Cl ( 7 b )) are attached to only one phosphorus atom, and spirocyclic 1,3-dichalcogena-2-phospha-[3]ferrocenophanes are formed. All new products have been characterized on the basis of their ¹ H, ¹³ C and ³¹ P NMR as well as EI mass spectra. The molecular structures of 5 a , b and 6 a have been determined by x-ray structure analyses.     

Synthese und Kristallstruktur von [Se3N2Cl]+ GaCl4−

Synthesis and Crystal Structure of [Se₃N₂Cl]⁺GaCl₄^? [Se₃N₂Cl]⁺GaCl₄^? has been prepared by the reduction of [Se₂NCl₂]⁺GaC1₄^? with SbPh₃ in CH₂Cl₂ solution, forming red crystals, which were characterized by an X-ray structure determination. Space group P2₁/n, Z = 4, 1640 observed unique reflections, R = 0.050. Lattice dimensions at ? 80 °C: a = 929.4(1), b= 1078.8(1), c = 1135.7(1) pm, β = 92.026(9)°. The cations from nearly planar Se₃N₂ five membered rings with Se? N bond lengths from 170 to 176pm and a Se? Se bond of 242.2 pm. One of the selenium atoms is bonded to the chlorine atom.     

Reaktionen des (Pentafluorsulfanyl)dichloramin

Reactions of Pentafluorosulfanyldichloroamine The previously unexplored reaction chemistry of pentafluorosulfanyldichloroamine has now led to the novel compounds SF₅N?PCl₃ and SF₅N?SeCl₂. Even though both compounds are produced in high yield (>80%), they were found to decompose readily at room temperature. SF₅NCl₂ has also been found to react with S₂Cl₂ or SCl₂ to give SF₅N?SCl₂, and with SF₅N?SCl₂ to give SF₅N?S?NSF₅. Finally, the adduct SF₅NH₂ · HCl is formed from SF₅NCl₂ and HCl.     

Bildung siliciumorganischer Verbindungen. 98. Umsetzung silylierter Phosphorylide mit PCl3

Formation of Organosilicon Compounds. 98. Reaction of Silylated Phosphorus Ylides with PCl₃ The reaction of Si-substituted phosphorus ylides as Me₂Si(CH₂? SiMe₂)₂C?PMe₃Br 1 , Cl₂Si(CH₂? SiCl₂)₂C?PMe₂Cl 2 , and (Cl₃Si)₂C?PMe₂Cl 3 with PCl₃ yields (Cl₂P)₂C?PMe₂Cl 5 by chlorinating cleavage of the Si-ylid-C bond. Besides 5 also (ClMe₂SiCH₂)₂SiMe₂, (Cl₃SiCH₂)₂SiCl₂, resp. SiCl₄ result from the reaction of 1, 2 and 3 with PCl₃. (Cl₂P)₂C?PMe₂Cl forms colourless crystals, mp. 84°C.