Die IR-Spektren von [Cr(O2)2(NH3)3] und K3[Cr(O2)2(CN)3]

The infrared spectra of the title compounds are reported and discussed. The influence of the peroxide groups on the bond properties of the other ligands and some characteristics of the metal—peroxide interactions are analyzed.     

Bildung und struktur der Cyclophosphane P4(CMe3)2[P(CMe3)2]2 und P4(SiMe3)2[P(CMe3)2]2

Formation and Structure of the Cyclophosphanes P₄(CMe₃)₂[P(CMe₃)₂]₂ and P₄(SiMe₃)₂[P(CMe₃)₂]₂ n-Triphosphanes showing a SiMe₃ and a Cl substituent at the atoms P¹ and P², like (Me₃C)₂P? P(SiMe₃)? P(CMe₃)Cl 3 or (Me₃C)₂P? P(Cl)? P(SiMe₃)₂ 4 are stable only at temperatures below ?30°C. Above this temperature these compounds lose Me₃SiCl, thus forming cyclotetraphosphanes, P₄(CMe₃)₂[P(CMe₃)₂]₂ 1 out of 3 , P₄(SiMe₃)₂[P(SiMe₃)₂]₂ 2a (cis) and 2b (trans) out of 4 . The formation of 1 proceeds via (Me₃C)₂P? P?PCMe₃ 5 as intermediate compound, which after addition to cyclopentadiene to give the Diels-Alder-adduct 6 (exo and endo isomers) was isolated. 6 generates 5 , which then forms the dimer compound 1 . Likewise (Me₃C)₂P? P?P-SiMe₃ 8 (as proven by the adduct 7 ) is formed out of 4 , leading to 2a (cis) and 2b (trans). Compound 1 is also formed out of the iso-tetraphosphane P[P(CMe₃)₂]₂[P(CMe₃)Cl] 9 , which loses P(CMe₃)₂Cl when warmed to a temperature of 20°C. 1 crystallizes monoclinically in the space group P2₁/a (no. 14); a = 1762.0(15) pm; b = 1687.2(18) pm; c = 1170.5(9) pm; β = 109.18(5)° and Z = 4 formula units in the elementary cell. The molecule possesses E conformation. The central four-membered ring is puckered (approx. symmetry 4 2m; dihedral angle 47.4°), thus bringing the substituents into a quasi equatorial position and the nonbonding electron pairs into a quasi axial position. The bond lengths in the four-membered ring of 1 (d (P? P) = 222.9 pm) are only slightly longer than the exocyclic bonds (221.8 pm). The endocyclic bond angles \documentclass{article}\pagestyle{empty}\begin{document}$ \bar \beta $\end{document}(P/P/P) are 85.0°, the torsion angles are ±33° and d (P? C) = 189.7 pm.     

Preparation of 2(3)-O-[2-(hydroxyamino)-2-oxoethyl]- and 2(3)-O-[3-(hydroxyamino)-3-oxopropyl]dextran

Hydroxame derivatives of carboxymethyl- and carboxyethyldextrans have been prepared and characterized by elemental analysis as well as by IR and UV spectroscopy. The effect of reaction conditions on the products yield has been studied.     

Isopropylammonium Layered Uranyl Chromates: Syntheses and Crystal Structures of [(CH3)2CHNH3]3[(UO2)3(CrO4)2O(OH)3] and[(CH3)2CHNH3]2[(UO2)2(CrO4)3(H2O)]

Two novel isopropylamine‐templated uranyl chromates, [(CH₃)₂CHNH₃]₃[(UO₂)₃(CrO₄)₂O(OH)₃] ( 1 ) and [(CH₃)₂CHNH₃]₂[(UO₂)₂(CrO₄)₃(H₂O)] ( 2 ) were prepared by hydrothermal method at 100 °C. The compounds were characterized by electron microprobe analysis and X‐ray diffraction crystal structure analysis [ 1 : trigonal, P31m, a = 9.646(4), c = 8.469(4) Å, V = 682.4(5) ų; 2 : monoclinic, P2₁/c, a = 11.309(3), b = 11.465(3), c = 17.055(5) Å, β = 99.150(6)°, V = 2183.2(11) ų]. The structure of 1 is based upon trimers of uranyl bipyramids interlinked by CrO₄ tetrahedra to form [(UO₂)₃(CrO₄)₂O(OH)₃]^3– layers, whereas, in the structure of 2 , UO₇ and UO₆(H₂O) pentagonal bipyramids are linked through CrO₄ tetrahedra into the [(UO₂)₂(CrO₄)₃(H₂O)]^2– layers. The structures show many similarities to related uranyl selenate compounds, thus providing additional data on similarities and differences between uranyl sulfates, chromates, selenates, and molybdates.     

Das iso-Tetraphosphan P[P(SiMe3)Me]2[P(SiMe3)2]

H ? C Bond Cleavage in Ferrocene by Organylruthenium Complexes Cp*(Me₃P)₂RuCH₂CMe₃ ( 1 ) reacts at 85°C with ferrocene ( 2 ) by cleavage of one H? C bond in 2 to give CpFe[η⁵-C₅H₄Ru(PMe₃)₂Cp*] ( 3 ) (Cp = η⁵-C₅H₅; Cp* = η⁵-C₅Me₅) and neopentane. The ruthenium atom in 3 has a distorted tetrahedral geometry, the planar Cp ligands in the ferrocenyl fragment are eclipsed. Solutions of 3 in [D₆]benzene or [D₈]THF exhibit H? D exchange of the ferrocenyl protons. In the [D₈]THF molecule only the α-deuterium atoms are exchanged. Reaction pathways for this exchange are discussed.     

Phosphaniminato-Komplexe von Bor. Synthese und Kristallstrukturen von [BBr2(NPMe3)]2, [B2Br3(NPiPr3)2]Br, [B2(NPEt3)4]Br2, [B2Br2(NPPh3)3]BBr4 und [{B2(NMe2)2}2(NPEt3)2]Cl2

Phosphoraneiminato Complexes of Boron. Syntheses and Crystal Structures of [BBr₂(NPMe₃)]₂, [B₂Br₃(NPⁱPr₃)₂]Br, [B₂(NPEt₃)₄]Br₂, [B₂Br₂(NPPh₃)₃]BBr₄ and [{B₂(NMe₂)₂}₂(NPEt₃)₂]Cl The bromoderivatives of the title compounds are prepared from the corresponding silylated phosphoraneimines Me₃SiNPR₃ and boron tribromide. The boron subcompound [{B₂(NMe₂)₂}₂(NPEt₃)₂]Cl₂ derives from Me₃SiNPEt₃ and B₂Cl₂(NMe₂)₂. All complexes are characterized by NMR and IR spectroscopy as well as by crystal structure determinations. [BBr₂(NPMe₃)]₂ (1): Space group P2₁/n, Z = 2, R = 0.031. Lattice dimensions at ?50°C: a = 723.8, b = 894.2, c = 1305.4 pm, β = 92.35°. 1 forms centrosymmetric molecules in which the boron atoms are linked via μ₂-N bridges of the NPMe₃^? groups of from B₂N₂ four-membered rings with B? N distances of 149.9 and 150.9 pm. B₂Br₃(NPⁱPr₃)₂]Br (2): Space group P2₁, Z = 2, R = 0.059. Lattice dimensions at ?80°C: a = 817.6, b = 2198.7, c = 851.5 pm, β = 115.09°. In the cations of 2 the boron atoms are lined via the μ₂-N atoms of the NPⁱPr₃^? groups to form planar, asymmetric B₂N₂ four-membered rings with B? N distances of 143 and 156 pm. [B₂(NPEt₃)₄[Br₂·4CH₂Cl₂ (3): Space group C2/c, Z = 4, R = 0.042. Lattice dimensions at ?50°C: a = 1946.1, b = 1180.3, c = 2311.3 pm, β = 101.02°. The structure contains centrosymmetric dications in which both the boron atoms are lined by the N atoms of two of the NPEt₃^? groups to form a B₂N₂ four-membered ring with B? N distances of 149.6 pm. The remaining two NPEt₃^? groups are terminally bonded with very short B? N distances of 133.5 pm. B₂Br₂(NPPh₃)₃]BBr₄ (4): Space group P1 , Z = 2, R = 0.065. Lattice dimension at ?50°C: a = 1025.7, b = 1496.1, c = 1807.0 pm, α = 85.09°, β = 82.90°, γ = 82.72°. In the cation the boron atoms are lined via the μ₂-N atoms of two of the NPPh₃^? groups to form a nearly planer B₂N₂ four-membered ring with B? N distances of 149.3-153.1 pm. The third NPPh₃³ group is terminally connected with teh sp² hybridized boron atom and with a B? N distance of 134.1 pm along with an almost linear BNP bond angle of 173.6°. [{B₂(NMe₂)₂}₂(NPEt₂)₂]Cl₂ · 3CH₂Cl₂ (5): Space group C2/c, Z = 4, R = 0.098. Lattice dimensions at ?70°C: a = 1557.9, b = 1294.7, c = 2122.9 pm, β = 96.08°. The structure of 4 contains centrosymmetric dications in which two by two B-B dumb-bells are linked via the μ₂-N atoms of the two NEPt₃^? groups to form B₄N₂ six-membered rings with B? N distances of 150 and 156 pm and B-B distances of 173 pm. The B? N distances of the terminally bonded NMe₂^? groups correspond to 138 pm double bonds.     

Isotype Strukturen einiger Hexaamminmetall(II)-halogenide von 3d-Metallen: [V(NH3)6]I2, [Cr(NH3)6]I2, [Mn(NH3)6]Cl2, [Fe(NH3)6]Cl2, [Fe(NH3)6]Br2, [Co(NH3)6]Br2 und [Ni(NH3)6]Cl2

The Structures of some Hexaammine Metal(II) Halides of 3 d Metals: [V(NH₃)₆]I₂, [Cr(NH₃)₆]I₂, [Mn(NH₃)₆]Cl₂, [Fe(NH₃)₆]Cl₂, [Fe(NH₃)₆]Br₂, [Co(NH₃)₆]Br₂ and [Ni(NH₃)₆]Cl₂ Crystals of yellow [V(NH₃)₆]I₂ and green [Cr(NH₃)₆]I₂ were obtained by the reaction of VI₂ and CrI₂ with liquid ammonia at room temperature. Colourless crystals of [Mn(NH₃)₆]Cl₂ were obtained from Mn and NH₄Cl in supercritical ammonia. Colourless transparent crystals of [Fe(NH₃)₆]Cl₂ and [Fe(NH₃)₆]Br₂ were obtained by the reaction of FeCl₂ and FeBr₂ with supercritical ammonia at 400°C. Under the same conditions orange crystals of [Co(NH₃)₆]Br₂ were obtained from [Co₂(NH₂)₃(NH₃)₆]Br₃. Purple crystals of [Ni(NH₃)₆]Cl₂ were obtained by the reaction of NiCl₂ · 6H₂O and NH₄Cl with aqueous NH₃ solution. The structures of the isotypic compounds (Fm3 m, Z = 4) were determined from single crystal diffractometer data (see “Inhaltsübersicht”). All compounds crystallize in the K₂[PtCl₆] structure type. In these compounds the metal ions have high-spin configuration. The orientation of the dynamically disordered hydrogen atoms of the ammonia ligands is discussed.     

Reaktionen von ClS[OCH(CF3)2]3 und S[OCH(CF3)2]2 mit Phosphor(III)-Verbindungen

Reactions of ClS[OCH(CF₃)₂]₃ and S[OCH(CF₃)₂]₂ with Phosphorus(III) Derivatives The sulfurane ClS[OCH(CF₃)₂]₃ reacts with Me₃P to give the phosphonium salt [Me₃POCH(CF₃)₂]⁺Cl^?, in the case of (MeO)₃P products of an Arbuzov reaction are found: (MeO)₂P-(:O)OCH(CF₃)₂ and MeCl; the sulfurane is reduced to the sulfoxylate S[OCH(CF₃)₂]₂. The cyclic phosphite FP[OC(CF₃)₂C(CF₃)₂O] and P[OCH(CF₃)₂]₃ furnish derivatives of pentacoordinated phosphorus upon reaction with ClS[OCH(CF₃)₂]₃. The sulfoxylate S[OCH(CF₃)₂]₂ oxidises Me₃P, (MeO)₃P and P[OCH(CF₃)₂]₃ to form R₃P? O and R₃P? S (R = Me, OMe, OCH(CF₃)₂). The ether (CF₃)₂CHOCH(CF₃)₂ is isolated, too.     

Synthesen und Strukturen neuer amido- und imidoverbrückter Cobaltcluster: [Li(THF)2]3[Co3(μ2-NHMes)3Cl6] (1), [Li(DME)3]2[Co18(μ4-NPh)3(μ3-NPh)12Cl3] (2), [Li(DME)3]2[Co6(μ4-NPh)(μ2-NPh)6(PPh2Et)2] (3) und [Li(THF)4][Co8(μ3-NPh)6(μ2-NPh)3(PPh3)2] (4)

Syntheses and Crystal Structures of new Amido- und Imidobridged Cobalt Clusters: [Li(THF)₂]₃[Co₃(μ₂-NHMes)₃Cl₆] (1), [Li(DME)₃]₂[Co₁₈(μ₄-NPh)₃(μ₃-NPh)₁₂Cl₃] (2), [Li(DME)₃]₂[Co₆(μ₄-NPh)(μ₂-NPh)₆(PPh₂Et)₂] (3), and [Li(THF)₄][Co₈(μ₃-NPh)₆(μ₂-NPh)₃(PPh₃)₂] (4) The reactions of cobalt(II)-chloride with the lithium-amides LiNHMes and Li₂NPh leads to an amido-bridged multinuclear complex [Li(THF)₂]₃[Co₃(μ₂-NHMes)₃Cl₆] ( 1 ) as well as to the imido-bridged cobalt cluster [Li(DME)₃]₂[Co₁₈(μ₄-NPh)₃(μ₃-NPh)₁₂Cl₃] ( 2 ). In the presence of tertiary phosphines two imido-bridged cobalt clusters [Li(DME)₃]₂[Co₆(μ₄-NPh)(μ₂-NPh)₆(PPh₂Et)₂] ( 3 ) and [Li(THF)₄][Co₈(μ₃-NPh)₆(μ₂-NPh)₃(PPh₃)₂] ( 4 ) result. The structures of 1 – 4 were characterized by X-ray single crystal structure analysis.     

Xenon Trioxide Adducts of O-Donor Ligands; [(CH3)2CO]3XeO3, [(CH3)2SO]3(XeO3)2, (C5H5NO)3(XeO3)2, and [(C6H5)3PO]2XeO3

Xenon trioxide (XeO₃) forms adducts with triphenylphosphine oxide, dimethylsulfoxide, pyridine-N-oxide, and acetone by coordination of the ligand oxygen atoms to the Xe^VI atom of XeO₃. The crystalline adducts were characterized by low-temperature, single-crystal X-ray diffraction, and Raman spectroscopy. Unlike solid XeO₃, which detonates when mechanically or thermally shocked, solid (C₅H₅NO)₃(XeO₃)₂, [(C₆H₅)₃PO]₂XeO₃, and [(CH₃)₂SO]₃(XeO₃)₂ are insensitive to mechanical shock. The [(CH₃)₂SO]₃(XeO₃)₂ adduct slowly decomposes over several days to (CH₃)₂SO₂, Xe, and O₂. All three complexes undergo rapid deflagration when ignited by a flame. Both [(C₆H₅)₃PO]₂XeO₃ and (C₅H₅NO)₃(XeO₃)₂ are room-temperature stable and the [(CH₃)₂CO]₃XeO₃ complex dissociates at room temperature to form a stable solution of XeO₃ in acetone. The xenon coordination sphere of [(C₆H₅)₃PO]₂XeO₃, a distorted square-pyramid, provides the first example of a five-coordinate XeO₃ complex with only two Xe- - -O adduct bonds. The xenon coordination spheres of the remaining adducts are distorted octahedra, comprised of three Xe- - -O secondary bonds that are approximately trans to the primary Xe−O bonds of XeO₃. Quantum-chemical calculations were used to assess the nature of the Xe- - -O adduct bonds, which are described as predominantly electrostatic bonds between the nucleophilic oxygen atoms of the bases and the σ-holes of the electrophilic xenon atoms.     

Die darstellung von [(CH3)3PRu(CO)2Cl2]2 und [(Ch3)3P]2Ru(CO)2Cl2; Eine berichtigung zu: Die alkoholyse des triethylsilans katalysiert von [(Ch3)3P]2Ru(CO)2Cl2

The ruthenium(II) complex used as a catalyst in reactions of alcohols and Et₃SiH proved to be the dimer [(CH₃)₃PRu(CO)₂Cl₂]₂ and not the complex [(CH₃)₃P]₂ Ru(CO)₂Cl₂. Both complexes were prepared, characterized and their catalytic properties were compared.     

[Zn3(PO4)2(H2O)0.8(NH3)1.2]

The structure of the title compound, ammineaquadi‐μ₅‐phosphato‐trizinc(II), [Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2], consists of two parts: (i) PO₄ and ZnO₄ vertex‐sharing tetrahedra arranged in layers parallel to (100) and (ii) ZnO₂(N/O)₂ tetrahedra located between the layers. Elemental analysis establishes the ammine‐to‐water ratio as 3:2. ZnO₂(N/O)₂ tetrahedra are located at special position 4e (site symmetry 2) in C2/c. The two O atoms of ZnO₂(N/O)₂ are bonded to neighbouring P atoms, forming two Zn—O—P linkages and connecting ZnO₂(N/O)₂ tetrahedra with two adjacent bc plane layers. A noteworthy feature of the structure is the presence of NH₃ and H₂O at the same crystallographic position and, consequently, qualitative changes in the pattern of hydrogen bonding and weaker N/O—H...O electrostatic interactions, as compared to two closely related structures.     

Phosphaniminato‐Komplexe des Zirconiums: Die Kristallstrukturen von [ZrCl3(NPPh3)(HNPPh3)2] und [ZrCl2(NPPh3)2(HNPPh3)2]

Phosphoraneiminato Complexes of Zirconium: Crystal Structures of [ZrCl₃(NPPh₃)(HNPPh₃)₂] and [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] The phosphoraneiminato complexes [ZrCl₃(NPPh₃)(HNPPh₃)₂] ( 1 ) and [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] ( 2 ) have been obtained by reaction of [ZrCl₄(THF)₂] with [CsNPPh₃]₄ in THF solution to give colourless moisture sensitive crystals which are characterized by X‐ray structure determinations. [ZrCl₃(NPPh₃)(HNPPh₃)₂] ( 1 ): Space group P 1, Z = 2, lattice dimensions at 193 K: a = 1209.4(2); b = 1480.8(2); c = 1814.2(2) pm; α = 71.203(13)°, β = 71.216(13)°, γ = 74.401(13)°; R = 0.0476. The zirconium atom of 1 is oktahedrally coordinated by the three chlorine atoms in meridional arrangement and by the three nitrogen atoms of the (NPPh₃^–) ligand and of the two phosphane imine molecules HNPPh₃. The ZrN bond distance of the (NPPh₃^–) group (193.5 pm) corresponds with a double bond. [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] ( 2 ): Space group P 1, Z = 4, lattice dimensions at 193 K: a = 1447.6(2); b = 1925.7(2), c = 2457.0(2) pm; α = 67.317(12)°, β = 87.376(12)°, γ = 87.103(13)°; R = 0.0408. The zirconium atom in 2 is octahedrally coordinated by the two chlorine atoms in trans position, and by the nitrogen atoms of the two (NPPh₃^–) groups as well as by the two HNPPh₃ molecules. The ZrN distance of the (NPPh₃^–) ligands (198.9 and 202.0 pm) suggest some π‐interaction between the zirconium and the nitrogen atoms.     

Kernresonanzspektroskopische Untersuchungen an cis-(CH3)2Pt[P(OCH3)3]2

100 MHz ¹ H n.m.r. spectra of cis-(CH₃)₂Pt[P(OCH₃)₃]₂ are analysed in full detail as superimposing [AR₃X₉]₂ and [AR₃X₉]₂M systems. The cis structure is derived from J(PP) and J(PtP).     

Umsetzung von C(NMe2)4 mit Ni(CO)4 – Synthesen und Strukturen von [C(NMe2)3][(CO)3NiC(O)NMe2], [C(NMe2)3]2[Ni5(CO)12] und [C(NMe2)3]3[Ni6(CO)12][O2CNMe2]

Reaction of C(NMe₂)₄ with Ni(CO)₄ – Syntheses and Structures of [C(NMe₂)₃][(CO)₃NiC(O)NMe₂], [C(NMe₂)₃]₂[Ni₅(CO)₁₂], and [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] The reaction of C(NMe₂)₄ with Ni(CO)₄ in THF produces the carbamoyl complex [C(NMe₂)₃][(CO)₃NiC(O)NMe₂] ( 1 ); side products are the purple cluster compound [C(NMe₂)₃]₂[Ni₅(CO)₁₂] · THF ( 2 · THF) and the red cocristallization product [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] ( 3 ). All compounds were studied by X‐ray diffraction analyses. The cations of 3 are all disordered but not those of 1 and 2 . The unit cell of 1 contains two crystallographically independent anions (I and II) which differ in the dihedral angle between the plane of the carbamoyl ligand and the plane defined by the atoms C_Carbamoyl–Ni–CO amounting 0° in the anion I and 18° in the anion II.     

Phase diagrams for the [Th(NO3)4(TBP)2]-decane-[UO2(NO3)2(TBP)2] liquid ternary system

We report a phase diagram (on the mole fraction scale) for the [Th(NO₃)₄(TBP)₂]-decane-[UO₂(NO₃)₂(TBP)₂](1-2-3) ternary liquid system, where TBP stands for tributyl phosphate, at T = 298.15 K. This system is characterized by a homogeneous solution field and a two-liquid field (immiscibility field); one phase (phase I) is enriched in [Th(NO₃)₄(TBP)₂] and [UO₂(NO₃)₂(TBP)₂], and the other (phase II) is enriched in decane. Molecular interaction parameters and excess Gibbs energies G ^ex were calculated for the binary systems and the ternary liquid system along the binodal curve proceeding from miscibility in the [Th(NO₃)₄(TBP)₂]-decane system and the ternary system and using equations of the NTRL model. For the ternary system, G ^ex > 0. G ^ex decreases in the following order of pairs of liquids: (1, 2) > (2, 3) > (1, 3).