Chemie polyfunktioneller Moleküle. 93. Die halogenierende Ringspaltung des As3-Nortricyclans, 4-Methyl-1,2,6-triarsatricyclo[2.2.1.02,6]heptan Darstellung und Eigenschaften von 2,6-Dihalogen-4-methyl-1,2,6-triarsabicyclo[2.2.1]heptanen

Chemistry of Polyfunctional Molecules. 93. Halogenating Ring Cleavage of As₃-Nortricyclane 4-Methyl-1,2,6-triarsatricyclo[2.2.1.0^2,6]heptane. Preparation and Properties of 2,6-Dihalogeno-4-methyl-1,2,6-triarsabicyclo[2.2.1]heptanes The reaction of the As₃-nortricyclane CH₃C(CH₂As)₃ ( 1 ) with PCl₅, Br₂, or I₂ in a molar ratio of 1:1 leads to the new 2,6-dihalogeno-4-methyl-1,2,6-triarsabicyclo[2.2.1]heptanes CH₃C(CH₂As)₃X₂ (X = Cl, Br, I; 2a–c ). Application of a molar ratio of 1:2 results in the formation of 1,1,1-tris(dihalogenoarsinomethyl)ethanes CH₃C(CH₂AsX₂)₃ ( 4a–c ) in rather poor yields; ¹H-NMR spectroscopic studies suggest that 4a–c are formed via 2a–c and the tetrahalogenodiarsacyclopentane derivatives ( 3a–c ); the latter can not be isolated from their solutions. 4a–c are obtained in very good yields by treatment of 1 with the halogenating agents in a molar ratio of 1:3 Comproportionation of 1 with 4a–c (molar ratio of 2:1) gives also 2a–c . Whereas in CD₂Cl₂ or CS₂ disproportionation of 2a leads to an equilibrium between 1 and 4a , which is formed via the intermediate 3a . The homologues 2b, c are stable with respect to disproportionation in both solvents.     

Chemie polyfunktioneller Moleküle, 94 Chrom- und Wolfram-pentacarbonylderivate des 4-Methyl-1,2,6-triphosphatricyclo[2.2.1.02,6]heptans (P3-Nortricyclans)

The P₃-nortricyclane 4-methyl-1,2,6-triphosphatricyclo[2.2.1.0^2,6]heptane, CH₃C(CH₂P)₃, (1), is synthesized in a better yield than earlier described from P₄, a Na/K alloy, and CH₃C(CH₂Br)₃ in boiling 1,2-dimethoxyethane. It reacts withM(CO)₅ thf (M=Cr, W) in the molar ratios of 1:1, 1:2, and 1:3 to form the pentacarbonylmetal complexes CH₃C(CH₂P)₃[M(CO)₅] _n [n=1, 2, 3;M=Cr (a), W (b)], (2 a, b–4 a, b).1 gives with Mo(CO)₅ thf only mixtures of CH₃C(CH₂P)₃[Mo(CO)₅] _n andcis-Mo(CO)₄ derivatives, which were identified by their infrared active A₁ v(CO) modes at 2075 and 2025 cm^–1.All the new compounds have been characterized also by their¹H{³¹P},³¹P{¹H} NMR, IR,Raman, and mass spectra.

     

Chemie polyfunktioneller Moleküle. 103 [1]: Chrom-, Molybdän- und Wolframtetra- sowie -tricarbonyl-Komplexe eines Diphenylphosphin-substituierten Cyclophosphamide

Inhaltsübersicht. (Ph₂PCH₂CH₂)₂N-P(O)N(H)CH₂CH₂CH₂O ( 2 ) bildet mit cis-M(CO)₄(C₇H₈) bzw. fac-M(CO)₃(CH₃CN)₃ (M = Cr, Mo, W; C₇H₈ = Norbornadien) die Chelat-komplexe cis-M(CO)₄(PPh₂CH₂CH₂)₂N-P(O)N(H)CH₂CH₂CH₂O ( 3a–c ) bzw. fac-M(CO)₃(PPh₂CH₂CH₂)₂N–P(O)N(H)CH₂CH₂CH₂O ( 4a–c ). 3a kristallisiert mit einem Mol Methanol aus, während 4a–c jeweils ein halbes Mol THF als Solvat enthalten. Alle Verbindungen wurden, soweit möglich, durch IR-, Raman-, ¹H-NMR-, ³¹P-NMR-, ¹³C-NMR- und Massenspektren charakterisiert. Chemistry of Polyfunctional Molecules. 103. Chromium, Molybdenum, and Tungsten Tetra- and Tricarbonyl Complexes of a Diphenylphosphine-substituted Cyclophosphamide Abstract. (Ph₂PCH₂CH₂)₂N–P(O)N(H)CH₂CH₂CH₂O (2) forms with cis-M(CO)₄(C₇H₈) or fac-M(CO)₃(CH₃CN)₃ (M = Cr, Mo, W; C₇H₈ = norbornadiene) the chelate complexes cis-M(CO)₄(PPh₂CH₂CH₂)₂N–P(O)N(H)CH₂CH₂CH₃O ( 3a–c ) or fac-M(CO)₃(PPh₂CH₂CH₂)₂N–P(O)N(H)CH₂CH₂CH₂O ( 4a–c ). 3a crystallizes with one mole of methanol whereas 4a–c contain 1/2 mole of THP as solvate. All compounds were, as far as possible, characterized by their IR, Raman, ¹H NMR, ³¹P NMR, ¹³C NMR, and mass spectra.     

Chemie polyfunktioneller Moleküle. 101 [1]: Synthese eines Diphenylphosphin-substituierten Cyclophosphamide und Röntgenstrukturanalyse seines Oxidations-produkts

Inhaltsübersicht. Diphenylphosphin und rac-Cyclophosphamid (ClCH₂CH₂)₂NP(O)N(H)(CH₂)₃O (1) reagieren in Gegenwart von n-Butyllithium zu einem Zwischenprodukt, das mit Wasser das diphenylphosphinsubstituierte Cyclophosphamid, (Ph₂PCH₂CH₂)₂NP(O)N(H)(CH₂)₃O, (2) bildet. Metallierung von 2 mit n-BuLi am N(3)-Atom und Umsetzung mit D₂O führt zum N(3)-Deuteroderivat 2a. Mit H₂O₂ reagiert 2 zur all-Phosphinoxid Verbindung, [Ph₂P(O)CH₂CH₂]₂NP(O)N(H)(CH₂)₃O, (4), die mit 0,5 Mol Wasser auskristallisiert und von der zur Charakterisierung des H-Bückenbindungssystems eine Röntgenstrukturanalyse angefertigt wurde. Die NMR-Spektren (¹H, ¹³C, ³¹P, ¹⁴N) weisen 2–4 als dynamische Moleküle aus. Chemistry of Polyfunctional Molecules. 101. Synthesis of a Diphenylphosphinesubstituted Cyclophosphamide and the X-ray Diffraction of its Oxidation Product Diphenylphosphine and rac-cyclophosphamide, (ClCH₂CH₂)₂NP(O)N(H)(CH₂)₃O, (1) react in the presence of n-BuLi to an intermediate which hydrolyses to the diphenylphosphine substituted Cyclophosphamide, (Ph₂PCH₃CH₂)₂NP(O)N(H)(CH₂)₃O, (2). Metallation of 2 with n-BuLi at the N(3) atom, followed by treatment with D₂O yields the N(3)-deuterated derivative 2a. With H₂O₂ 2 forms the all-phosphine-oxide compound, [Ph₂P(O)CH₂CH₂]₂NP(O)N(H)(CH₂)₃O, ( 4 ), which crystallizes with 0.5 mole of water. In order to characterize the H-bridge bonding system a X-ray structure analysis of 4 was carried out. The NMR-Spectra (¹H, ¹³C, ³¹P, ¹⁴N) indicate 2–4 as dynamic molecules.     

Synthese und Reaktionen von Bicyclo[6.4.0]dodecan-3-carbonsäure-Derivaten

Synthesis and Reactions of the Bicyclo[6.4.0]dodecane-3-carboxylic Acid Derivatives The synthesis and some consecutive reactions of the compounds 5-8 , derivatives of bicyclo[6.4.0]dodecane-3-carboxylic acid ( 1 ), are described. The esters 7 and 8 can be obtained by Baeyer-Villiger oxidation of 2-hydroxy-8-methyltricyclo[7.3.1.0^2,7]tridecan-13-one ( 4 ) and subsequent hydrolysis of the lactone 5 . The structure and configuration of these compounds has been evaluated by spectroscopic techniques (mainly 2D-NMR methods). The formation of 7 via 1,2-H shift and subsequent isomerization to 8 has been studied. The esters 11 and 13 are formed stereospecifically from 7 and 8 .     

Hydrogendiazid Synthese und Kristallstruktur von PPh4[N3HN3]

Hydrogen Diazide – Synthesis and Crystal Structure of PPh₄[N₃HN₃] PPh₄[N₃HN₃] has been prepared from PPh₄N₃ and Me₃SiN₃ by the reaction with water or ethanol forming colourless nonexplosive crystal needles, which were characterized by IR spectroscopy and by a crystal structure determination. Space group C2/c, Z = 12, lattice dimensions at –70 °C: a = 3782.4(3), b = 727.8(2), c = 2512.4(2) pm, β = 110.13(1)°, R = 0.0841. The [N₃HN₃]^– ion is characterized by an asymmetric N–H…N hydrogen bridge with a NN distance of 272(1) pm.     

Chemie polyfunktioneller Moleküle. 118 [1]. Synthesen und Kristallstrukturanalysen von bicyclischen Metallaphosphazenen des Platins und Eisens mit vier- und sechsgliedrigen Ringen

Chemistry of Polyfunctional Molecules. 118. Syntheses and Crystal Structures of Bicyclic Metallaphosphazenes with Four and Six Membered Rings Anhydrous MCl₂ (M = Pt, Fe) react with LiN(PPh₂)₂ ( 1 ) in the molar ratio of 1:2 in boiling toluene within 25 hours under partially oxidative scrambling of the PNP chain in 1 yielding the bicyclic metallaphosphazenes 5 a, b . While compound 5 a can be isolated in substance, the intermediate 5 b proves to be highly reactive but can be stabilized in the presence of CO, forming the 18-valence-electron coordination compound as an isomeric trans( 6 a )/cis( 6 b ) mixture in the molar ratio of 99:1. Also treatment of anhydrous PtCl₄ with four equivalents of 1 in boiling toluene during 60 hours yields 5 a . Alkylation of 5 a with CH₃I leads to the formation of the ionic species [Pt²⁺{Ph₂P? N(CH₃)? PPh₂}(Ph₂P? N = PPh₂ = N? PPh₂^?)]I^? ( 9 ). The X-ray crystal structures of 5 a × 1 CH₂Cl₂ and 6 a reveal, that the metal centres have a planar P-coordination polyhedron in the solid state. In the complex 9 × 2,5 CH₂Cl₂ however the torsion angle between the P? Pt? P planes of the four and six membered rings shows to be 15°. The six membered metallacycles in 5 a × 1 CH₂Cl₂, 6 a and 9 × 2,5 CH₂Cl₂ differ in their geometrical arrangement. All the new compounds have also been characterized by their ¹H, ³¹P{¹H}, ¹³C{¹H} NMR, IR, Raman and mass spectra.     

Synthese und Kristallstrukturen von NH4[Si(NH3)F5] und [Si(NH3)2F4]

Synthesis and Crystal Structures of NH₄[Si(NH₃)F₅] and [Si(NH₃)₂F₄] Single crystals of NH₄[Si(NH₃)F₅] and [Si(NH₃)₂F₄] are obtained by reaction of silicon powder with NH₄HF₂ in sealed Monel ampoules at 400°C. NH₄[Si(NH₃)F₅] crystallizes with the tetragonal space group P4/n (no. 85) with a = 614.91(7) pm, c = 721.01(8) pm, Z = 2. Characteristic for the structure is the anionic octahedron [Si(NH₃)F₅]^?. Si(NH₃)₂F₄ crystallizes with the monoclinic space group P2₁/c (no. 14) with a = 506.9(1) pm, b = 728.0(1) pm, c = 675.9(1), β = 93,21(2)°, Z = 2. Trans-[Si(NH₃)₂F₄] molecules are characteristic for this structure.     

Synthese und Struktur von (PPh4)3[Re2NCl10]

Synthesis and Crystal Structure of (PPh₄)₃[Re₂NCl₁₀] The rhenium(V) nitrido complex (PPh₄)₃[Re₂NCl₁₀] ( 1 ) is obtained from the reaction of (PPh₄)[ReNCl₄] with 1, 3‐dioxan‐(2‐ylmethyl)diphenyl phosphine in CH₂Cl₂/CH₃CN in form of orange red crystals with the composition 1 ·2CH₂Cl₂ crystallizing in the triclinic space group P1¯ with a = 1210.7(2), b = 1232.5(1), c = 2756.3(5) pm, α = 99.68(1)°, β = 100.24(1)°, γ = 98.59(1)° and Z = 2. The crystal structure contains two symmetry independent, centrosymmetrical complex anions [Re₂NCl₁₀]^3‐ with a symmetrical nitrido bridge Re=N=Re and distances Re(1) ‐ N(1) = 181.34(5) and Re(2) ‐ N(2) = 181.51(4) pm.     

Die Einwirkung von Ammoniumfluorid auf Scandium: Synthese und Kristallstrukturen von (NH4)3[ScF6] und [Cu(NH3)4]3[ScF6]2

Action of Ammonium Fluoride on Scandium: Synthesis and Crystal Structures of (NH₄)₃[ScF₆] and [Cu(NH₃)₄]₃[ScF₆]₂ The action of (NH₄)F on scandium in copper ampoules yields either (NH₄)₃[ScF₆] or ScF₃ and a small quantity of [Cu(NH₃)₄]₃[ScF₆]₂, respectively, depending upon the molar ratio of the educts (NH₄)F : Sc (6 : 1 and 4 : 1, respectively) and temperature. (NH₄)₃[ScF₆] crystallizes with the cryolite type of structure: monoclinic, P2₁/n, Z = 2; a = 650.0(2); b = 651.4(2); c = 949.0(2) pm; β = 90.40(2)°, [Cu(NH₃)₄]₃[ScF₆]₂ is triclinic, P‐1, Z = 1; a = 821.1(2); b = 821.2(2); c = 822.7(2) pm; α = 90.04(3); β = 90.00(3); γ = 90.16(3)°. In its chemical behaviour against (NH₄)F, scandium parallels aluminium rather than gallium.     

Das Reaktionsverhalten von Cp2NbCl2 gegenüber WF6—Struktur von [Cp2NbCl2]4[WF6]2[WCl6]

The oxidation of Cp₂NbCl₂ with pure WF₆ in SO₂ solution yielded the cationic metallocene species [Cp₂NbCl₂]⁺[WF₆]⁻ essentially in quantitative yield. The same reaction carried out in the presence of either equimolar amounts or a two-fold excess of HCN led to the preparation of the new niobocenium salt [Cp₂NbCl₂]₄⁺[WF₆]²⁻ which was studied by single crystal X-ray diffraction. This compound represents the first example of a structurally characterized metallocene-WF₆⁻ complex, and crystallizes in the tetragonal system: space group, P4₁2₁2(No. 92), a = 11.083(8) Å, c = 48.285 (9) Å; Z = 8; R = 0.0759, R_W = 0.0841. ab]Die Oxidation von Cp₂NbCl₂ mit reinem WF₆ führt in SO₂-Lösung zur Synthese von [Cp₂NbCl₂ ]⁺[WF₆]⁻ in nahezu quantitativer Ausbeute. Die analoge Reaktion führt unter Anwesenheit der äquimolaren Menge oder eines zweifachen Überschusses an HCN zur Ausbildung des Niobocenium-Komplexsalzes [Cp₂NbCl₂]₄⁺ [WF₆]₂⁻[WCl₆]²⁻, von dem eine Röntgenstrukturanalyse angefertigt wurde. Diese Verbindung repräsentiert den ersten structurell charakterisierten Vertreter eines Metallocen-WF₆⁻-Komplexes und kristallisiert im tetragonalen System: Raumgruppe P4₁2₁2 (Nr. 92), a = 11.083(8) Å, c = 48.285(9) Å; Z = 8; R = 0.0759, R_W = 0.0841. kw]Niobium; X-ray diffraction; Oxidation; Metallocenes     

Synthese von 5,6-Dimethyl-4-oxo-1,3,4,5-tetrahydro-imidazo-[4,5-c] [1,2,6]thiadiazin-2,2-dioxid und 7-Methyl-4-oxo-1H-3,4-dihydro-pyrimido[4,5-c][1,2,6]thiadiazin-2,2-dioxid

Synthesis of 5,6-Dimethyl-4-oxo-1,3,4,5-tetrahydro-imidazo[4,5-c][1,2,6]thiadiazin 2,2-dioxide and 7-Methyl-4-oxo-1H-3,4-dihydropyrimido[4,5-c][1,2,6]thiadiazin 2,2-dioxide The derivatives of the above heterocyclic ring systems were prepared by reaction of the corresponding o-amino esters with sulfamoylchloride.     

Die kristall- und molekülstruktur von Fe3Te2(CO)9

The crystal and molecular structure of Fe₃Te₂(CO)₉ has been determined by X-ray diffraction analysis. The compound crystallizes in the triclinic space group P$\text{1}$ with a 952.5(4), b 1314.3(8), c 694.7(2) pm, α 95.27(4), β 112.78(3), γ 81.44(4)° and Z = 2 (R = 0.036, using 2079 reflections).     

Synthese,Struktur und Thermolyse von NH4[Re3Br10]

Synthesis, Structure and Thermolysis of NH₄[Re₃Br₁₀] NH₄[Re₃Br₁₀] crystallizes as dark brown single crystals upon slow cooling of a hot, saturated hydrobromic-acid solution of [Re₃Br₉(H₂O)₂] after the addition of NH₄Br. The crystal structure (monoclinic, C2/m (Nr. 12); Z = 4; a = 1461.6(7), b = 1 085.6(4), c = 1030.3(7) pm, β = 92.63(4)°, V_m = 245.9(4)cm³/mol; R = 0.097, R_w = 0.043) contains [Re₃Br₁₂]^? units that share two common edges. These chains run along [010] and are held together by NH₄⁺ ions. Each NH₄⁺ is surrounded by eight Br^? from four different chains. The first step of the thermal decomposition at 290°C is the disproportionation to ReBr₃ (ReCl₃ type), rhenium metal and (NH₄)₂[ReBr₆]. Secondly, the internal reduction of (NH₄)₂[ReBr₆] at 390°C to rhenium metal takes place.     

Synthese und Kristallstrukturen von [Ti(NPh2)4] und [Ti2(μ-O)(NPh2)6]

Crystal Structures of [Ti(NPh₂)₄] and [Ti₂(μ-O)(NPh₂)₆] [Ti(NPh₂)₄] has been prepared from TiCl₃(THF)₃ and LiNPh₂, the μ-oxo complex [Ti₂(μ-O)(NPh₂)₆] results from partial hydrolysis of [Ti(NPh₂)₄] in toluene solution. Both complexes are characterized by crystal structure determinations. In [Ti(NPh₂)₄] the titanium atom is coordinated by the four nitrogen atoms in a distorted tetrahedral fashion with Ti–N bond lengths of 193.8 pm in average. In [Ti₂(μ₂-O)(NPh₂)₆] the μ-oxo ligand forms a linear symmetric TiOTi bridge with rTiO = 181.2 pm and TiN = 193.4 pm in average.     

Über Thallium(I)-chlorooxomolybdate: Synthese und Kristallstrukturen von Tl[MoOCl4(NCCH3)], Tl[Mo2O2Cl7] und Tl2[Mo4O4Cl14] und die Struktur von Tl2[MoCl6]

On Thallium(I)-oxochloromolybdates: Synthesis and Crystal Structures of Tl[MoOCl₄(NCCH₃)], Tl[Mo₂O₂Cl₇], and Tl₂[Mo₄O₄Cl₁₄] and the Structure of Tl₂[MoCl₆] Black crystals of Tl₂[MoCl₆] are formed in the reaction of TlCl with MoOCl₃ in a sealed evacuated glass ampoule at 350 °C. The crystal structure analysis shows that Tl₂[MoCl₆] (cubic, Fm 3¯m, a = 986.35(7) pm) adopts the K₂[PtCl₆] structure with a Mo–Cl bond length of 236.6 pm. Tl[MoOCl₄(NCCH₃)] was obtained by the reaction of TlCl with MoOCl₃ in acetonitrile in form of yellow, moisture sensitive crystals. The structure (orthorhombic, Cmcm, a = 746.0(1), b = 1463.8(3), c = 857.3(2) pm) is built of Tl⁺ cations and octahedral [MoOCl₄(NCCH₃)]^– anions in which the acetonitrile ligand is bound in trans position to the oxygen. The reaction of TlCl and MoOCl₃ in dichloromethane yields Tl[Mo₂O₂Cl₇] and Tl₂[Mo₄O₄Cl₁₄] as green moisture sensitive crystals. The structure of Tl[Mo₂O₂Cl₇] (orthorhombic, Pmmn, a = 694.3(1), b = 951.9(2), c = 904.7(1) pm) consists of Tl⁺ cations and dinuclear [Mo₂O₂Cl₇]^– anions, with two equidistant chlorine bridges of 248.2 and one longer chlorine bridge of 265.7 pm. The oxygen atoms are located in the trans positions of the longer chloro bridge. The structure of Tl₂[Mo₄O₄Cl₁₄] (triclinic, P1¯, a = 692.8(1), b = 919.6(1), c = 998.9(1) pm, α = 104.94(1)°, β = 90.31(1)°, γ = 108.14(1)°) is build of Tl⁺ cations and [Mo₄O₄Cl₁₄]^2– anions which form tetramers of distorted octahedral, edgesharing (MoOCl₅) units with chlorine atoms in the bridging positions. The oxygen atoms are located in the trans positions of the longest chlorine bridges.