Triethylphosphanimin-Komplexe der Acetate von Kupfer(II) und Zink. Kristallstrukturen von [Zn(O2C–CH3)2(HNPEt3)], [Cu5(O2C–CH3)10(HNPEt3)2] und [Cu(O2C–CH3)2(HNPEt3)2]

Triethylphosphanimine Complexes of the Acetates of Copper(II) and Zinc. Crystal Structures of [Zn(O₂C–CH₃)₂(HNPEt₃)], [Cu₅(O₂C–CH₃)₁₀(HNPEt₃)₂], and [Cu(O₂C–CH₃)₂(HNPEt₃)₂] The title compounds originate from the anhydrous acetates of zinc and copper(II) with trimethylsilyl-triethylphosphanimine, Me₃SiNPEt₃, in the presence of water in dichloromethane. They form colourless ( 1 ), bluish-green ( 2 ), and blue ( 3 ), respectively, single crystals, which were characterized by IR spectroscopy and by crystal structure analyses. [Zn(O₂C–CH₃)₂(HNPEt₃)] ( 1 ): Space group P 4 2₁c, Z = 8, lattice dimensions at –83 °C: a = b = 1709.6(2), c = 982.4(1) pm, R = 0.0551. 1 has a polymeric chain structure in which the zinc atoms are μ₂-bridged via the oxygen atoms of one of the two acetato groups, while the second acetato group and the phosphanimine are bonded terminally. [Cu₅(O₂C–CH₃)₁₀(HNPEt₃)₂]( 2 · 4 CH₂Cl₂): Space group P2₁/c, Z = 8, lattice dimensions at –80 °C: a = 1761.18(13), b = 4074.5(2), c = 1733.34(15) pm, β = 91.383(10)°, R = 0.0413. 2 consists of the two structural units [Cu₂(O₂C–CH₃)₄] and [Cu₃(O₂C–CH₃)₆(HNPEt₃)₂], which are connected via two of the acetato groups of the Cu₃-unit along the crystallographic a-axis to form three crystallographically independent polymeric strands. [Cu(O₂C–CH₃)₂(HNPEt₃)₂] ( 3 ): Space group P2₁/n, Z = 2, lattice dimensions at 20 °C: a = 695.49(8), b = 1217.85(10), c = 1380.05(7) pm, β = 96.451(7)°, R = 0.0291. 3 forms monomeric, centrosymmetric molecules with a square planar environment at the Cu atoms.     

Schwingungsspektren und Kraftkonstanten der Übergangsreihen OP(N(CH3)2)3 – OP(CH3)3 und SP(N(CH3)2)3 – SP(CH3)3

Vibrational Spectra and Force Constants of the Series OP(N(CH₃)₂)₃ – OP(CH₃)₃ and SP(N(CH₃)₂)₃ – SP(CH₃)₃ The vibrational spectra (IR and Raman) of the compounds of the title series are recorded and assigned to the normal vibrations. By a simplified force field the valence force constants are calculated and discussed. The results are compared with those of the NMR spectroscopy.     

Über die Systeme Arsen(III)-chlorid–Arsen(III)-oxid und Arsen(III)-chlorid–Wasser (AsCl3 – As2O3 und AsCl3 – H2O)

In the system AsCl₃ – As₂O₃ are found the crystalline solids AsOCl and As₄O₅Cl₂, in the system AsC1₃–H₂O: As₄O₆ and AsOCl. The phase diagram AsCl₃–H₂O is determined at 20°C.     

Ammonium hydrogen squarate–water (3/2)

In the title compound, NH₄⁺·C₄HO₄^?·H₂O, the hydrogen squarate anions and water molecules are arranged to form planes almost parallel to bc. The ammonium cations are located between these planes and cross‐link them in the a direction by means of an extensive network of hydrogen bonds. There are two symmetry‐independent sets of cations and anions. One of the hydrogen squarate anions and one of the ammonium cations are situated on a twofold axis and the H atoms of these moieties are disordered over the symmetry‐related sites.     

(CH3)2SBr2 – einige Reaktionen und Strukturen

(CH₃)₂SBr₂ – Reactions and Structures (CH₃)₂SBr₂ ( 1 ) is a donor acceptor complex (8-S-3 + 10-Br-2) which reacts with (CH₃)₂S(?O)NSi(CH₃)₃ to yield [(CH₃)₂S(O)?N? S(CH₃)₂]⁺Br^? ( 2 ). With SbBr₃ (CH₃)₂SBr⁺SbBr₄^? ( 3 ) can be isolated. 1 crystallizes monoclinic in the space group P2₁/c with a = 733.8, b = 734.2, c = 1132.7 pm, β = 92.8° and Z = 4. 2 crystallizes in the orthorhombic space group Pnma with a = 967.2, b = 793.3, c = 1168.3 pm and Z = 4. The SBr and BrBr force constants of 1 are compared with those of S₂Br₂, 3 and Br₂ resp. The nmr and mass spectra of 1 and 2 are communicated.     

[Cs(Toluol)3(FIn{N(SiMe3)2}3)], ein Fluoroindat mit gestreckter Cs–F–In-Achse

[Cs(toluene)₃(FIn{N(SiMe₃)₂}₃)], a Fluoroindate with Rectified Cs–F–In Axis The metalate [Cs(FIn{N(SiMe₃)₂}₃)] has been prepared by the reaction of In[N(SiMe₃)₂]₃ with CsF in THF: The title compound 1 can be obtained by recrystallization from toluene as colorless airsensitive needles. 1 has been characterized by NMR-, IR-, and MS-techniques as well as by an X-ray structure determination. The result of the structure analysis shows an prolated molecule with an almost linear Cs–F–In axis [174.7(1)°]. The Cs⁺ center is surrounded by the indate ion and three toluene molecules in a distorted tetrahedral fashion.     

Die Reaktionen von tBu2P–P=P(Me)tBu2 und (Me3Si)tBuP–P=P(Me)tBu2 mit PR3

The Reactions of ^tBu₂P–P=P(Me)^tBu₂ and (Me₃Si)^tBuP–P=P(Me)^tBu₂ with PR₃ ^tBu₂P–P=P(Me)^tBu₂ ( 1 ) reacts at 20 °C with PMe₃, PEt₃, P(c‐Hex)₃, P(p‐Tol)₃, PPh₂Me, PPh₂Et, PPhEt₂, PPh₂ⁱPr, PPh₃ and P(NEt₂)₃ yielding ^tBu₂P–P=PR₃ and ^tBu₂PMe; however, P^tBu₃, P^tBu₂(SiMe₃) and ^tBu₂PCl don't. ^tBu₂PH and 1 form ^tBu₂P–PH–P^tBu₂ which yields ^tBu₂P–P=PEt₃ when treated with PEt₃. Ph₂PH, ^tBuPH₂, PH₃, Ph₂PCl and EtOH don't substitute the ^tBu₂PMe group in 1 , instead, the molecule is decomposed. With PEt₃, (Me₃Si)^tBuP–P=P(Me)^tBu₂ forms (Me₃Si)^tBuP–P=PEt₃. The compounds ^tBu₂P–P=PR₃ decompose at 20 °C to different degrees giving P‐rich consecutive products of the phosphinophosphinidene.     

Syntheses of Trifluoromethanethiolato Platinum(II) Complexes – Crystal Structures of cis‐Pt(SCF3)2(PPh3)2 and trans‐Pt(SCF3)Cl(PPh3)2

Ligand exchange reactions of cis‐PtCl₂(PPh₃)₂ and [NMe₄]SCF₃ in different ratios were studied. Depending on the stoichiometry reactions proceeded with formation of products expected for the chosen ratio, i. e. cis‐Pt(SCF₃)Cl(PPh₃)₂, cis‐Pt(SCF₃)₂(PPh₃)₂, and [NMe₄][Pt(SCF₃)₃(PPh₃)]. Starting from cis‐PtCl₂(MeCN)₂ and [NMe₄]SCF₃ and adding PPh₃ after substitution, product mixtures were dominated by the corresponding trans‐isomers. Results of the single crystal structure analyses of cis‐Pt(SCF₃)₂(PPh₃)₂ and trans‐Pt(SCF₃)Cl(PPh₃)₂ are discussed.     

Li(VO2)3(TeO3)2

The title compound, lithium tris[dioxidovanadium(V)] bis[trioxidotellurium(IV)], contains chains of edge‐sharing distorted VO₆ octahedra. The pyramidal TeO₃ groups crosslink the chains into sheets. Finally, an Li⁺ cation adopting an unusual capped trigonal–bipyramidal LiO₆ geometry bridges the layers to complete a three‐dimensional structure.     

[In3(In2)3(PhP)4(Ph2P2)3Cl7(PEt3)3]– A New Molecular III/V Compound Featuring an Unusual 19-Atom Cage

Near C ₃ symmetry is displayed by the 19-atom In-P polyhedron that forms the central structural unit in the title compound (see structure), which was synthesized by reaction of InCl₃ with PEt₃ and PhP(SiMe₃)₂. In addition to In–P bonds, the cage has In–In and P–P bonds. Six terminal chloro ligands and three PEt₃ ligands surround the cluster core which itself encloses a central chloride anion.     

F2P(NEt2)3 – Difluorphosphorane als vielseitige Fluoridierungsmittel

F₂P(NEt₂)₃ – Difluorophosphanes as Versatile Fluoridation Agent F₂P(NEt₂)₃ ( 1 ), prepared by the reaction of P(NEt₂)₃ with SF₄ (3:2) in Et₂O at –78°C, acts as fluoridation agent on Lewis acids such as AlMe₃, GaMe₃, or [Mes₃V(THF)] by transfer of a F ^– ion. The products [FP(NEt₂)₃][Me₃MF] [M = Al ( 2 ), Ga ( 3 )] and [FP(NEt₂)₃][Mes₃VF] ( 4 ) were characterized by NMR, IR and MS techniques. With 1 and 4 an X‐ray structure determination could be performed. According to them 1 consists of trigonal‐bipyramidal λ⁵‐phosphane molecules with an occupation of the axial positions by F^– ligands. In 4 the centers of the cations [FP(NEt₂)₃]⁺ and of the anions [Mes₃VF]^– are distorted terahedrally coordinated.     

Using Me3Si–F–Al(ORF)3 and Me3Si–Cl as Methylating Agents – Synthesis and Characterization of SeMeCl2[F{Al(ORF)3}2]

Upon reacting SeCl₄ with Me₃Si–F–Al(OR^F)₃, the selenonium salt SeMeCl₂[al‐f‐al] ( 1 ) {[al‐f‐al]^– = [F[Al(OC(CF₃)₃)₃]₂]^–} was obtained and characterized by NMR, IR, and Raman spectroscopy as well as single crystal XRD experiments. Despite the [SeX₃]⁺ (X = F, Cl, Br, I) and [SeR₃]⁺ salts (R = aliphatic organic residue) being well known and thoroughly studied, the mixed cations are scarce. The only previous example of a salt with the [SeMeCl₂]⁺ cation is SeMeCl₂[SbCl₆], which was never structurally characterized and is unstable in solution over hours. Only ¹H‐NMR studies and IR spectra of this compound are known. The unexpected use of Me₃Si–F–Al(OR^F)₃ as a methylating agent was investigated via DFT calculations and NMR experiments of the reaction solution. The reaction of SeCl₃[al‐f‐al] with Me₃Si‐Cl at room temperature in CH₂Cl₂ proved to yield the same product with Me₃Si–Cl acting as a methylating agent.     

Schwingungsspektren und Kraftkonstanten der Übergangsreihen OP (CH3)3–OP(OCH3)3 und SP(CH3)3–SP(OCH3)3

Vibrational Spectra and Force Constants of the Series OP(CH₃)₃? OP(OCH₃)₃ and SP(CH₃)₃? SP(OCH₃)₃ The vibrational spectra of OP(CH₃)₂(OCH₃), OP(CH₃)(OCH₃)₂, SP(CH₃)₂(OCH₃), and SP(CH₃)(OCH₃)₂, are recorded and assigned to the normal vibration. The valence force constants are calculated by a simplified force field. The results are disscussed for both series and compared with former results.     

CsMoO2(HO3P–CH2–PO3): a new metallodiphosphonate with a hybrid framework

Crystals of caesium molybdeno­methyl­enedi­phospho­nate, [CsMoO₂(CH₃O₆P₂)], were hydro­thermally synthesized at 473 K. The monoclinic structure, as determined from single‐crystal X‐ray diffraction, is two‐dimensional and consists of stacked mixed layers of corner‐sharing tetrahedral di­phosphon­ate groups and MoO₆ octahedra, between which Cs⁺ cations are intercalated.