Molekül- und Kristallstruktur von 9λ4-Thia-2,4,6,8,10,11-hexaza-1λ5,3λ5,5λ5,7λ5-tetraphosphabicylo[5.3.1]undeca-1,3,5,7(11),8,9-hexaen,einem schwefeldiimidoüberbrückten Cyclotetraphosphazen

Molecular and Crystal Structure of 9λ⁴-Thia-2,4,6,8,10,11-hexaaza-1λ⁵,3λ⁵,5λ⁵,7λ⁵-tetraphosphabicylo[5.3.1]undeca-1,3,5,7(11),8,9-hexaene, Cyclotetraphosphazene Bridged by a Sulfur Diimide Group We have carried out an X-ray structure analysis of the title compound ( 1 ). 1 crystallizes in the monoclinic space group P2₁/b with a = 9.436(4), b = 20.102(7), c = 11.622(5) Å, γ = 103.52(8)°, Z = 8. There are two molecules in the asymmetric unit, which in approximation can be transformed one into the other by additional symmetry elements of a substructure of a space group B2/b. The S = N bond lengths are 1.53 Å. The P? N bonds connecting the SN₂ system are 1.666 Å long. They are significantly longer than the P? N multible bonds in the P₄N₄ ring within a range of 1.517 to 1.565 Å. The sulfur diimide unit and its substituents are coplanar causing a half-boat conformation of the heterocyclic six membered ring. The cyclotetraphosphazene ring shows a flattened crown-saddle conformation, the phosphorous atoms arranged nearly at the corners of a square. Influenced by crystal packing there exist small deviations from the molecular mirror plane and also differences in conformation between the two molecules of the asymmetric unit.     

Synthese und Struktur von S{NAs(tBu)2[Os3(CO)11]}2 Das erste Schwefeldiimid mit trans,trans-Konfiguration im Festkörper

Synthesis and Structure of S{NAs(^tBu)₂[Os₃(CO)₁₁]}₂. The First Sulphur Diimide with trans,trans Configuration in the Solid State In the reaction of bis(di-tert-butylarsino) sulphur diimide, S(NAs^tBu₂)₂, with the cluster Os₃(CO)₁₁(NCCH₃) either one or two [Os₃(CO)₁₁] units can be added to the sulphur diimide — according to the molar ratio — yielding Os₃(CO)₁₁As(^tBu)₂NSNAs^tBu₂ ( 1 ) or S{NAs(^tBu)₂[Os₃(CO)₁₁]}₂ ( 2 ), respectively. The title compound μ-[(trans,trans)-bis(di-tert-butyl-arsino)sulphur diimide-As,As]-bis(undecacarbonyl-triangulo-triosmium) ( 2 ) is also obtained upon thermolysis of 1 in refluxing octane; its structure was elucidated by X-ray crystallography. Complex 2 is the first sulphur diimide with a trans,trans configuration in solid state. The trans,trans configuration is forced by the bulky substituents. 2 crystallises with deuterochloroform (1:1) in the monoclinic space group C2/c: a = 25.887(3), b = 8.684(1), c = 26.357(4) Å, β = 103.34(1)°, Z = 4. Due to special positions the SN₂ moiety (inversion center) and the chloroform molecule (twofold axis) are disordered statistically. The S?N bond lengths amount 1.50(2) Å on the average, the angle at, sulphur (111(2)°) is smaller in comparison with open-chained sulphur diimides with the cis, trans and cis,cis configuration. The angles a t the K atoms are enlarged (131(2) and 135(2)°), respectively. With exception of small torsions around the S?N bonds the principle of coplanarity for sulphur diimides is also fulfilled for t,he trans, trans form. The amino residues occupy equatorial positions in the triosmium clusters. I n the triosmium triangle two bonds are almost equal in length (2.891(1) and 2.884(1) Å, respectively), the third Os? Os bond is somewhat enlarged (2.939(1) Å).     

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).     

1λ6,2,4-Thiadiazetidine und 1,2λ6,3-Oxathiazetidine

1λ⁶,2,4-Thiadiazetidines and 1,2λ⁶,3-Oxathiazetidines From the reaction of the sulfur triimides (RN?)₃S ( 2a R?(CH₃)₃C, 2b R?(CH₃)₃Si) with pentafluoroazapropene ( 11 ) the appropriate 1λ⁶,2,4 thiadiazetidines ( 13a, 13b ) are formed, while from ClSO₂N?CCl₂ ( 14 ) and 2a (CH₃)₃C? N?C?N? SO₂Cl ( 17 ) is isolated. 2b and hexafluoroacetone ( 18 ) give the rather unstable 1,2λ⁶,3-oxathiazetidine ( 20 ).     

Cyclotri(λ3-phosphazane) (XPNMe)3: Darstellung,NMR-Spektren und Struktur

Ausgehend vom trihalogensubstituierten Cyclotri(λ³-phosphazan) 1 lassen sich die Derivate 2—12 in glatter Reaktion darstellen. Die sterische Belastbarkeit des Sechsring-systems hat mit X = NEt₂ in 11 ihre Grenze erreicht, für X = N? iPr₂ tritt nur noch Monosubstitution zu 13 ein, die aber eine Weitersubstitution mit sterisch weniger anspruchsvollen Resten, z. B. auch zu den Bicyclen 14—16 nicht ausschließt. Die NMR-spektroskopischen Daten legen eine Sesselkonformation der Cyclophosphazanringe nahe, wobei die diequatorial-axiale bzw. diaxial-equatoriale Konfiguration der Phosphoratome ( c, d ) als thermodynamisch günstigere Alternative zu a oder b verwirklicht ist. Es wird erstmals über eine Ringkontraktion vom Sechs- zum Vierring in der Reihe der Cyclo(λ³-phosphazane) berichtet. Cyclotri(λ³-phosphazanes) (XPNMe)₃: Preparation, NMR-Data, and Structure Cyclotri(λ³-phosphazanes) 2–12 are easily prepared from the trihalogeno substituted 1 . For steric reasons there is only a monosubstitution with X = N? iPr₂ to 13 , which nevertheless may be further substituted by sterically less demanding substituents to give e.g. the bicyclic compounds 14—16 . From NMR spectroscopic data a chair conformation of the six membered ring seems probable with the substituents at phosphorus being located either diequatorially axially ( c ) or vice versa ( d ) rather than a or b . A thermal ring contraction from a six to a four membered ring in the series of cyclo(λ³-phosphazanes) is reported for the first time.     

Acyl- und Alkylidenphosphane. XXIV. (N,N-Dimethylthiocarbamoyl)trimethylsilylphosphane und 1,2-Di(tert-butyl)-3-dimethylamino-1-thio-4-trimethylsilylsulfano-1λ5,2λ3-diphosphet-3-en

Acyl- and Alkylidenephosphines. XXIV. (N,N-Dimethylthiocarbamoyl)trimethylsilyl-phosphines and 1.2-Di(tert-butyl)-3-dimethylamino-1-thio-4-trimethylsilylsulfano-1λ⁵, 2λ³-diphosphet-3-ene In contrast to bis(trimethylsilyl)phosphines R? P[? Si(CH₃)₃]₂ 1 {R ? H₃C a ; (H₃C)₃C b ; H₅H₆ c ; H₁₁C₉ d ; (H₃C)₃Si e }, the more nucleophilic lithium trimethylsilylphosphides 4 react with N,N-dimethylthiocarbamoyl chloride already at ?78°C to give (N,N-dimethylthiocarbamoyl)trimethylsilylphosphines 2 . Working up the reaction, a dismutation of the mesityl derivative 2d is observed, whereas the tert-butyl compound 2b dissolved in toluene, eliminates dimethyl(trimethylsilyl)amine to form 1,2-di(tert-butyl)-3-dimethylamino-1-thio-4-trimethylsilyl-sulfano- 1λ⁵, 2λ³-diphosphet-3-ene 6b , nearly quantitatively within several days at +20°C.     

From Isolated Polyanions to 1‐D Structure: Synthesis and Crystal Structure of Hybrid Fluorides {[(C2H4NH3)3NH]4+}2 · (H3O)+ · [Al7F30]9– and {[(C2H4NH3)3NH]4+}2 · [Al7F29]8– · (H2O)2

Two new hybrid fluorides, {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · (H₃O)⁺ · [Al₇F₃₀]^9– ( I ) and {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · [Al₇F₂₉]^8– · (H₂O)₂ ( II ), are synthesized by solvothermal method. The structure determinations are performed by single crystal technique. The symmetry of both crystals is triclinic, sp. gr. P 1, I : a = 9.1111(6) Å, b = 10.2652(8) Å, c = 11.3302(8) Å, α = 110.746(7)°, β = 102.02(1)°, γ = 103.035(4)°, V = 915.9(3) ų, Z = 1, R = 0.0489, R_w = 0.0654 for 2659 reflections, II : a = 8.438(2) Å, b = 10.125(2) Å, c = 10.853(4) Å, α = 106.56(2)°, β = 96.48(4)°, γ = 94.02(2)°, V = 877.9(9) ų, Z = 1, R = 0.0327, R_w = 0.0411 for 3185 reflections. In I , seven corner‐sharing AlF₆ octahedra form a [Al₇F₃₀]^9– anion with pseudo 3 symmetry; such units are found in the pyrochlore structure. The aluminum atoms lie at the corners of two tetrahedra, linked by a common vertex. In II , similar heptamers are linked in order to build infinite (Al₇F₂₉)_n^8– chains oriented along a axis. In both compounds, organic moieties are tetra protonated and establish a system of hydrogen bonds N–H…F with four Al₇F₃₀^9– heptamers in I and with three inorganic chains in II .     

2‐Imino‐3‐allyl‐benzothiazole as a π‐Ligand: Synthesis and Crystal Structure of [(CuCl)C10H10SN2], [C10H11SN2+]2[Cu2Cl4]2−, and [C10H11SN2+]2[Cu2Br4]2− π‐Compounds

The reaction of 2‐amino‐benzothiazole with allyl bromide resulted in a mixture of 2‐imino‐3‐allyl‐benzothiazole and 2‐imino‐3‐allyl‐benzothiazolium bromide.Using such a mixture and copper(II) chloride in acetonitrile solution in alternating‐current electrochemical synthesis crystals of the [(CuCl)C₁₀H₁₀SN₂] ( I ) have been obtained. The same procedure, performed in ethanol solution, has led to formation of [C₁₀H₁₁SN₂⁺]₂[Cu₂Cl₄]^2? ( II ). In the same manner the bromine derivative [C₁₀H₁₁SN₂⁺]₂[Cu₂Br₄]^2? ( III ) has been synthesized. All three compounds were X‐ray structurally investigated. I :monoclinic space group P2₁/n, a = 13.789(6), b = 6.297(3), c = 13.830(6) Å, β = 112.975(4)°, V = 1105.6 (9) ų, Z = 4 for CuCl·C₁₀H₁₀ SN₂ composition. Compounds II and III are isomorphous and crystallize in triclinic space group. II a = 7.377(3), b = 8.506(3), c = 9.998(4) Å, α = 79.892(10)°, β = 82.704(13)°, γ = 78.206(12)°, V = 601.9(4) ų, Z = 1. III a = 7.329(2), b = 8.766(3), c = 10.265(3) Å, α = 79.253(9)°, β = 82.625(9)°, γ = 77.963(9)°, V = 630.9(3) ų, Z = 1. In the structure I [(CuCl)C₁₀H₁₀SN₂] building blocks are bound into infinitive spiral‐like chains via strong N‐H..Cl hydrogen bonds. In the zwitter‐ionic II and III compounds copper and halide atoms form centrosymmetric [Cu₂X₄]^2? anions, which are interconnected via N‐H..X hydrogen bonds into infinite butterfly‐like chains. The strongest Cu‐(C=C) π‐interaction has been observed in structure I , where copper possesses coordination number 3. Increasing copper coordination number to 4 in II as well as replacing chlorine atoms by bromine ones in III suppresses markedly this interaction.     

Kaliumamidotrioxogermanate(IV) – Wasserstoff-Brückenbindungen in K3GeO3NH2 und K3GeO3NH2 · KNH2

Potassium Amido Trioxo Germanates(IV) – Hydrogen Bridge Bonds in K₃GeO₃NH₂ and K₃GeO₃NH₂ · KNH₂ Colorless crystals of K₃GeO₃NH₂ and of K₃GeO₃NH₂ · KNH₂ were obtained by the reaction of KNH₂ with GeO₂ in supercritical ammonia at 450°C and p = 6 kbar in high-pressure autoclaves within 15 resp. 5 days. The crystal structures of both compounds were solved by X-ray single crystal methods. K₃GeO₃NH₂: P1 , a = 6.390(1) Å, b = 6.684(1) Å, c = 7.206(1) Å, α = 96.47(1)°, β = 101.66(1)°, γ = 91.66(1)°, Z = 2, R/R_w = 0.020/0.022, N(I) ≥ 2σ(I) = 3023, N(Var.) = 82 K₃GeO₃NH₂ · KNH₂: P2₁/c, a = 10.982(6) Å, b = 6.429(1) Å, c = 12.256(8) Å, β = 106.12(1)°, Z = 4, R/R_w = 0.022/0.029, N(F) ≥ 3σ(F) = 1745, N(Var.) = 107. In K₃GeO₃NH₂ tetrahedral ions GeO₃NH₂^3? are connected to chains by N? H …? O bridge bonds with 2.18 Å ≤ d(H …? O) ≤ 2.40 Å for d(N? H) ? 1.0 Å and by potassium ions while in K₃GeO₃NH₂ · KNH₂ bridge bonds between NH₂ groups of GeO₃NH₂^3? and NH₂^? ions as acceptors occur with 2.41 Å ≤ d((N? )H …? NH₂^?) ≤ 2.61 Å for d(N? H) ? 1.0 Å.     

Neue 1λ5, 3λ5-[1,3]Diphosphinine mit Thio- und Selenophosphonsäureresten – Darstellung,Kristallstruktur, NMR-Daten und Komplexbildung mit PdII

Diphosphabenzenes. VI. New 1λ⁵, 3λ⁵-[1,3]Diphosphinines with Thio and Seleno Phosphonic Acid Groups – Preparation, Crystal Structure, NMR Data, and Coordination to Pd^II Preparation of N,N,N′,N′-tetraethyl-P-phenylethinyl phosphonothioacid diamide ( 2 ) and the corresponding phosphonoselenoacid diamide ( 3 ) are described. 2 and 3 react with 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete ( 1 ) to yield 1λ⁵,3λ⁵-[1,3]diphosphinine derivatives 4 and 5 . With (bzl)₂Cl₂Pd 5 forms the coordination compound 6 . All new compounds 2–6 are characterized by their nmr and ir spectra, the structures of 4–6 are further elucidated by X-ray structural analyses.     

Heterodinukleare Komplexe: Synthese und Kristallstrukturen von [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)]

Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)], [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], and [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] [Ru₃Rh(CO)₇(μ₃‐H)(μ‐P^tBu₂)₂(^tBu₂PH)(μ‐Cl)₂] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) ų. The reaction of 4 with dppm (Ph₂PCH₂PPh₂) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 ų. Moreover single crystals of [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P2₁/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) ų.     

Beiträge zur Chemie von Phosphorverbindungen mit Adamantanstruktur. XIV. Kristallstruktur eines 3, 5-Diphenyl-1, 2, 4-dithiazolium-Salzes mit käfigförmigem [P4NS9]-Anion

Contributions to the Chemistry of Phosphorus Compounds with Adamantane Structure. XIV. Crystal Structure of a 3, 5-Diphenyl-1, 2, 4-dithiazolium Salt with the Cage-like Anion [P₄NS₉] The compound 3, 5-Diphenyl-1, 2, 4-dithiazolium 1, 3, 5, 7-pentathioxo-10-aza-2, 4, 6, 8, 9-pentathia-1α⁵,3λ⁵,5λ⁵,7λ⁵-tetraphosphatricyclo[3.3.1.1^3,7]decanide has been prepared by the reaction of P₄S₁₀ with benzonitrile. It crystallizes in the triclinic space group P1 with a = 9.914 Å, b = 15.025 Å, c = 9.186 Å, α = 100.48°, β = 99.90°, γ = 90.66°, and Z = 2. The anion has the structure of a P₄S₁₀-like cage, in which one P? S? P group is replaced by the P? N? P group.     

Preparation,spectral characterization,and single crystal X-ray structures of cis and trans isomers of 2,4,6-trifluoroethoxy-1,3,5-triethyl-1,3,5,2λ5, 4λ5, 6λ5-triazatriphosphorinane-2,4,6-trioxide, [ETNP(O)(OCH2CF3)]3

Oxidation of the cis isomer of the λ³-cyclotriphosphazane [EtNP(OCH₂CF₃)]₃ with trimethylamine-N-oxide (TMNO) gives the cis isomer of trioxo-λ⁵-cyclotriphosphazane [EtNP(O)(OCH₂CF₃)]₃; the trans isomer of [EtNP(O)(OCH₂CF₃)]₃ is obtained by the treatment of a cis and trans mixture of [EtNP(OCH₂CF₃)]₃ with aqueous H₂O₂. The two trioxocyclotriphosphazanes have been characterized by elemental analysis, IR, and NMR (¹H, ¹³C, ¹⁹F, and ³¹P) spectroscopy. The solid state structures of both the isomers have been determined by single crystal X-ray diffraction. The six-membered P₃N₃ ring in both the isomers exhibits a twist-boat conformation; in the cis isomer, the trifluoroethoxy substituents lie on the same side of the ring, whereas, in the trans isomer, two trifluoroethoxy groups are on one side of the ring and the third on the other side of the ring. Crystal data for cis-[EtNP(O)(OCH₂CF₃)]₃: monoclinic, P 2₁/ n , a = 13.593(3), b = 9.721(2), c = 17.539(3) Å, β = 99.49(2)°, V = 2286(1) ų, Z = 4, and Final R = 0.047. Crystal data for trans-[EtNP(O)(OCH₂CF₃)]₃: monoclinic, P 2₁/ n , a = 11.685(4), b = 15.115(5), c = 13.233(5) Å, - = 102.21(3)°, V = 2284(1) ų, Z = 4, and Final R = 0.078.     

Untersuchungen über S?H …︁ S-Wasserstoffbrücken Die Kristallstruktur der Diphenyldithiophosphinsäure bei 140 und 293 K

Die Kristallstruktur der Diphenyldithiophosphinsäure (C₆H₅)₂P(S)SH wurde röntgenographisch bei tiefer Temperatur und Normaltemperatur aus Einkristalldiffraktometerdaten bestimmt und bis zu R-Werten von 0,037 (140 K, (sin Θ)/λ < 0,81 Å^?1) und 0,035 (293 K, (sin Θ)/λ < 0,64 Å^?1) verfeinert. Die Verbindung kristallisiert in der monoklinen Raumgruppe P2₁/c mit den bei 140 K (in Klammern: 293 K) gemessenen Gitterkonstanten a = 9,824(3) (9,887), b = 10,061(3) (10,175), c = 14,342(4) (14,433) Å, β = 122,08(3) (121,73)° und V = 1201,1 (1234,9) ų, Z - 4. Im Kristall sind individuelle Moleküle über fast lineare S? H…?S-Wasserstoffbrückenbindungen zu schraubenförmig gewundenen Ketten verknüpft. Bei 140 K beträgt der S…?S-Abstand innerhalb der Brücke 3,790(1) Å; die weiteren geometrischen Daten der Wasserstoffbrücke sind: d(S? H): 1,25(2), d(S…?H): 2,56(2), d(P? S): 2,077(1), d(P?S): 1,954(1) Å, ? (S? H…?S): 169,5(14), ? (P? S…?S): 98,87(2), ? (P?S…?S): 96,65(2)°. Investigations on Compounds Containing S? H…?S Hydrogen Bonds. Crystal Structure of Diphenyldithiophosphinic Acid at 140 and 293 K The crystal structure of diphenyldithiophosphinic acid (C₆H₅)₂P(S)SH was determined from X-ray diffraction data collected at 140 and 293 K and was refined to R factors of 0.037 (140 K, (sin Θ)/λ < 0.81 Å^?1) and 0.035 (293 K, (sin Θ)/λ < 0.64 Å^?1) respectively. The compound crystallizes in the monoclinic space group P2₁/c with unit cell parameters at 140 K (in parentheses: at 293 K): a = 9.824(3) (9.887), b = 10.061(3) (10.175), c = 14.342(4) (14.433) Å, β = 122.08(3) (121.73)° and V = 1201.1 (1234.9) ų, Z = 4. In the crystalline state individual molecules are linked together by nearly linear S? H…?S hydrogen bonds so that endless helical chains are formed. At 140 K the S…?S distance within the hydrogen bond is 3.790(1) Å; the other distances and angles associated with the bridge are: d(S? H): 1,25(2), d(S…?H): 2,56(2), d(P? S): 2,077(1), d(P?S): 1.954(1) Å, ? (S? H…?S): 169.5(14), ? (P? S…?S): 98.87(2), ? (P? S…?S): 96.65(2)°.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

Übergangsmetall-Komplexe des 1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphets

Transition Metal Complexes of 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-Diphosphete 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3aλ⁵-diphosphete, 1 , reacts with W(CO)₆ to yield the isomeric complexes {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)tungsten 4 and {1,1,3,3-tetrakis(dimethylamino)-1,4-dihydro-1λ⁵,3λ⁵-[1,3]diphosphetium}(pentacarbonyl)tungsten 5 . With Cr(CO)₆ the complex {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)chromium 6 is formed. From the reaction products of Fe₃(CO)₁₂ and Fe₂(CO)₉ with 1 the complex {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)iron 7 could be isolated. Properties, nmr, ir and mass spectra of the new compounds are reported. 6 and 7 were characterized by X-ray structure determinations.     

Synthesis,Crystal Structure,and NMR Spectroscopy of a New P-Phenylenediamonium Diphosphate [p-NH3C6H4NH3]H2P2O7

Crystal growth and characterization by X-ray diffraction and NMR spectroscopy of a new p-phenylenediamonium diphosphate [p-NH₃ C ₆ H ₄ NH ₃]H ₂ P ₂ O ₇ are reported. This compound crystallizes in a triclinic unit cell P1 with the parameters a = 7.130(3), b = 9.047(3), c = 9.350(2) Å, α = 133.44(2)°, β = 95.02(2)°, γ = 107.11(4)°, Z = 2, V = 514.3(15) ų, and D _x = 1.848 g.cm^{? 3}. The crystal structure has been solved and refined to R = 0.0273, using 3678 independent reflections. The atomic arrangement is build up by infinite ribbons of [H₂ P ₂ O ₇] ^2? anions, extending along the a-direction at y = 1/2. Between these ribbons are located the p-phenylenediammonium entities, which form hydrogen bonds N─H…O with some external oxygen atoms of phosphoric groups. Crystallographic results are correlated with that of the solid state ¹³C and ³¹P MAS NMR spectroscopy.     

Synthese und NMR-Spektren von λ5-Diphospheten Die Struktur des 2,4-Diphenyl-1,1,3,3-tetrakis(diethylamino)-1λ5,3λ5-diphosphets

Synthesis and NMR Spectra of λ⁵-Diphosphets. Structure of 2,4-Diphenyl-1,1,3,3-tetrakis (diethylamino)-1λ⁵, 3λ⁵-diphosphete Preparation, properties, and n.m.r. spectra of C₂H₅PF₂[N(C₂H₅)₂]₂, CH₂?PF[N(C₂H₅)₂]₂, and the diphosphetes {RC?P[N(C₂H₅)₂]₂}₂ (R) ? H ( 5a ), CH₃ [( 5b )] are described. The λ⁵-diphosphete {HC?P(NR₂)₂}₂ (R ? CH₃) reacts with BF₃ · O(C₂H₅)₂ to give which is transformed into by n-C₄H₉Li. The crystal and molecular structure of 2,4-diphenyl-1,3,3-tetrakis(diethylamino)-1λ⁵,3λ⁵-diphosphete 2 are reported and discussed.     

Syntheses,and Crystal Structures of Indium Complexes with η2‐Piperidinyldithiocarbamate and η2‐Pyridine‐2‐Thionate Containing Ligands: Structures of [In(η2‐S2CNC5H10)3] and [In(η2‐pyS)3]

The η²‐thio‐indium complexes [In(η²‐thio)₃] (thio = S₂CNC₅H₁₀, 2 ; SNC₄H₄, (pyridine‐2‐thionate, pyS, 3 ) and [In(η²‐pyS)₂(η²‐acac)], 4 , (acac: acetylacetonate) are prepared by reacting the tris(η²‐acac)indium complex [In(η²‐acac)₃], 1 with HS₂CNC₅H₁₀, pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 : space group, C2/c with a = 13.5489(8) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) ų, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3 : space group, P2₁ with a = 8.8064 (6) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) ų, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine‐2‐thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C‐N bond length in the range of 1.322(4)–1.381(6) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character.     

Synthesis and Structures of New Oxidation/ Cycloaddition Products of λ3‐Cyclodiphosphazanes

Reaction of the cyclodiphosphazane [(OC₄H₈N)P(μ‐N‐t‐Bu)₂P(HN‐t‐Bu)] ( 1 ) with an equimolar quantity of diisopropyl azodicarboxylate afforded the phosphinimine product [(OC₄H₈N)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂ ‐i‐Pr)NHCO₂‐i‐Pr] ( 6 ) having a P^III‐N‐P^V skeleton. Similar products [(t‐BuNH)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂Et)NHCO₂Et] ( 7 ) and [(CO₂‐i‐Pr)HNN(CO₂‐i‐Pr)](t‐BuN=P(μ‐N‐t‐Bu)₂POCH₂CMe₂CH₂O[P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂‐i‐Pr)NH(CO₂‐i‐Pr)] ( 8 ) were spectroscopically characterized in the reaction of [(t‐BuNH)P‐N‐t‐Bu]₂ ( 2 ) and [(t‐BuNH)P(μ‐N‐t‐Bu)₂POCH₂CMe₂CH₂OP(μ‐N‐t‐Bu)₂P(NH‐t‐Bu)] ( 3 ) with diethyl‐ and diisopropyl azodicarboxylate, respectively. By contrast, the reaction of [(μ‐t‐BuN)P]₂[O‐6‐t‐Bu‐4‐Me‐C₆H₂]₂CH₂ ( 4 ) and [(C₅H₁₀N)P‐μ‐N‐t‐Bu]₂ ( 5 ) with diisopropyl azodicarboxylate afforded the mono‐ and bis‐oxidized compounds [(O)P(μ‐N‐t‐Bu)₂P][O‐6‐t‐Bu‐4‐Me‐C₆H₂]₂CH₂ ( 9 ) and [(C₅H₁₀N)(O)P‐μ‐N‐t‐Bu]₂ ( 10 ), respectively. Oxidative addition of o‐chloranil to 7 and its DIAD analogue [(t‐BuNH)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂‐i‐Pr)NHCO₂‐i‐Pr] ( 11 ) afforded [(C₆Cl₄‐1, 2‐O₂)(t‐BuNH)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂R)NHCO₂R] [R = Et ( 12 ) and i‐Pr ( 13 )] containing tetra‐ and pentacoordinate P^V atoms in the cyclodiphosphazane ring. The structures of 6 , 9 , 12 and 13 have been confirmed by X‐ray structure determination. For comparison, the X‐ray structure of the double cycloaddition product [(C₆Cl₄‐1, 2‐O₂)(t‐BuNH)PN‐t‐Bu]₂ ( 14 ), obtained from the reaction of 2 with two mole equivalents of o‐chloranil is also reported.