Gold-Stickstoff-Heterocyclen. Synthese,Eigenschaften und Struktur von [(CH3)2AuNH2]4 und [(CH3)2AuN(CH3)2]2

Gold Nitrogen Heterocycles. Synthesis, Properties, and Structure of [(CH₃)₂AuNH₂]₄ and [(CH₃)₂AuN(CH₃)₂]₂ Dimethyl gold iodide reacts with alkali metal amides to form Au-N heterocycles. KNH₂ yields the eight-membered ring [(CH₃)₂AuNH₂]₄, whereas with LiN(CH₃)₂ the four-membered ring [(CH₃)₂AuN(CH₃)₂]₂ is obtained. The light sensitive, cyclic gold amides are stable against hydrolysis and do not react with Lewis bases. [(CH₃)₂AuN(CH₃)₂]₂ crystallizes monoclinic in the space group P2₁/c with Z = 2. The molecules exhibit the symmetry D_2h. Symmetrical amido bridges form a planar Au-N heterocyclus with distances Au-N = 214 pm.     

Gold-Stickstoff-Heterocyclen. 2. Synthese,Eigenschaften und Struktur von N-Methylamidodimethylgold(III), [(CH3)2AuNHCH3]2

Gold Nitrogen Heterocycles 2. Synthesis, Properties, and Structure of N-Methyla nido Dimethyl Gold(III), [(CH₃)₂AuNHCH₃]₂ . The reaction of (CH₃)₂AuI with LiNHCH₃ yields dimeric N-methylamido dimethyl gold(III) besides small quantities of higher aggregates. [(CH₃)₂AuNHCH₃]₂ is an air-stable, white compound, which decomposes by irradiation with light. Monoclinic single crystals can be obtained by sublimation under vacuum. [(CH₃)₂AuNHCH₃]₂ crystallizes in the space group C2/c with the lattice constants a = 1751.7(8), b = 398,3(7), c = 1868.8(9) pm and β = 124.61(4)°. The unit cell contains four dimers with symmetry C_2v. In the bent four membered Au—N heterocyclus the Au atoms are linked together by symmetric amido bridges with Au? N distances of 214 pm. IR, H-NMR, and mass spectra are discussed.     

Synthese,Eigenschaften und Struktur von oktamerem Titanimidchlorid [Ti(NSiMe3)Cl2]8

Synthesis, Properties, and Structure of Octameric Titanium Imide Chloride [Ti(NSiMe₃)Cl₂]₈ The reaction of TiCl₄ with N(SiMe₃)₃ in sealed glas-tubes yields the titanium imide chloride [Ti(NSiMe₃)Cl₂]₈ ( 1 ). It crystallizes in the space group C2/c with a = 2 704.5(4), b = 1 303.9(1), c = 2 205.4(2) pm, β = 112.78(1)°, Z = 4. In 1 six Ti atoms are linked together by chloro and trimethylsilylimido bridges to form a ring structure. Two TiCl₂-groups are bound in addition to the ring by two imido bridges. Upon annealing at 250°C 1 transformes to the isomeric polymer [Ti(NSiMe₃)Cl₂]_n. Above 250°C 1 decomposes under separation of Me₃SiCl affording TiNCl.     

Synthese,Eigenschaften und Struktur von cis-Dihydridoazido-tris(triphenylphosphino)-iridium

Synthesis, Properties, and Structure of cis-Dihydrido Azido Tris(triphenylphosphino) Iridium cis-IrH₂(N₃)(PPh₃)₃ is formed from IrCl₃(PPh₃)₃ and NaN₃ in alcohol. The solvent transfers the hydride ions whereby aldehyde is formed. The creme-colored cis-IrH₂(N₃)(PPh₃)₃ is a diamagnetic low-spin complex. Exposure to light yields H₂ and Ir(N₃)(PPh₃)₃ in a reversible process. The cis position of the hydrido ligands is confirmed by the i.r. and H-N.M.R. spectra. Cis-IrH₂(N₃)(PPh₃)₃ crystallizes in the monoclinic system with the space group P2₁/c. The crystal structure exhibits isolated octahedral complexes, in which one hydrido ligand is located trans to the azido group. The other one being trans to one of the phosphine ligands.     

Synthese,Struktur und Eigenschaften von drei Tetranatrium-tetrametaphosphimat-Hydraten

Synthesis, Structure, and Properties of Three Tetrasodium Tetrametaphosphimate Hydrates Single crystals of three tetrasodium tetrametaphosphimate hydrates Na₄(PO₂NH)₄ · x H₂O with x = 2 and 3, respectively, have been obtained and characterized by single crystal X-ray diffraction. Dimorphous Na₄(PO₂NH)₄ · 3 H₂O is formed at RT. It crystallizes monoclinic ( 1 ) or triclinic ( 2 ) (α-Na₄(PO₂NH)₄ · 3 H₂O ( 1 ): P2₁, a = 1002.7(2), b = 1189.7(2), c=1193.1(2)pm, β=104.93(1)°, Z=4; β-Na₄(PO₂NH)₄ · 3 H₂O ( 2 ): P 1¯, a = 843.64(9), b = 848.54(10), c = 994.7(2) pm, α = 83.07(1), β = 76.31(1), γ = 87.46(1)°, Z = 2). Compound 2 is formed in the presence of NaCl during the crystallization from aqueous solution. Tetrasodium tetrametaphosphimate dihydrate ( 3 ) is formed at 60 °C (Na₄(PO₂NH)₄ · 2 H₂O ( 3 ): C2/c, a = 2225.6(3), b = 513.0(1), c = 1566.7(2) pm, β = 134.21(1)°, Z = 4). In 1 and 2 the P₄N₄ ring of the tetrametaphosphimate ions attains a saddle and in 3 a twistboat conformation. The conformations of the anions have been analysed using torsion angles, displacement asymmetry parameters, and puckering parameters. The (PO₂NH)₄^4– rings of the compounds 1 , 2 , and 3 are linked by N–H · · &mid     

Struktur und Eigenschaften von Methyltrifluorphosphoran CH3PF3H

Structure and Properties of Methyltrifluorophosphorane CH₃PHF3₃ Methyldichlorophosphane reacts with three equivalents of HF under formation of Methyltrifluorophosphorane, which is characterized by mass, NMR, and vibrational spectroscopy. The ab intio calculation (HF/6‐31+G*) yields a distorted trigonal bipyramidal structure for CH₃PF₃H. The methyl group (r P—C = 180.2 pm), the hydrogen (r P—H = 137.1 pm) and one fluorine atom (r P—F_eq = 155.8 pm) are located at equatorial positions. The P—F_ax‐distance is 163.4 pm. The Lewis‐amphoteric properties are shown by reactions with CsF, [(CH₃)₄]NF and AsF₅.     

Synthese,Eigenschaften und Struktur von [Li(OC4H8)4][((CH3)3Si)3C–InBr3]

Synthesis, Properties, and X-Ray Structure Determination of [Li(OC₄H₈)₄][((CH₃)₃Si)₃C–InBr₃] The reaction of InBr₃ with LiR* · (THF)_n (R* = –C(SiMe₃)₃, THF = OC₄H₈) in a 1 : 1 molar ratio forms [Li(THF)₄][R*InBr₃] in good yield. The properties and some spectroscopic data (¹H, ¹³C, ²⁹Si, ⁷Li–NMR, IR and Raman) of this trisyl-tribromoindate are given and the crystal structure has been determined.     

Synthese,Kristallstruktur und Magnetismus von [(CH3)2NH2][PrCl4(H2O)2]

Preparation, Crystal Structure, and Magnetism of [(CH₃)₂NH₂][PrCl₄(H₂O)₂] The complex water containing chloride [(CH₃)₂NH₂][PrCl₄(H₂O)₂] has been prepared for the first time and the crystal structure has been determined from single crystal X‐ray diffraction data. The compound crystallizes orthorhombically in the space group Cmca (Z = 8) with a = 1796.6(2) pm, b = 940.7(1) pm, and c = 1238.4(2) pm. The anionic part of the structure is built up by chains of edge‐connected trigondodecahedra [PrCl₆(H₂O)₂]^3– according to [PrCl_4/2Cl₂(H₂O)₂]^–, which are held together by dimethylammonium cations ([(CH₃)₂NH₂]⁺). In order to study the interactions between the praseodymium cation (Pr³⁺) and the ligands magnetic measurements were carried out. The magnetic data were interpreted by ligand field calculations applying the angular overlap model.     

Synthese,Kristallstruktur und Magnetismus von [(CH3)2NH2][NdCl4(H2O)2]

Preparation, Crystal Structure, and Magnetism of [(CH₃)₂NH₂][NdCl₄(H₂O)₂] The complex water containing chloride [(CH₃)₂NH₂][NdCl₄(H₂O)₂] was prepared for the first time and the crystal structure was determined by X‐ray methods from single crystals. The compound crystallizes in the orthorhombic space group Cmca (Z = 8) with a = 1793.5(2) pm, b = 936.6(2) pm and c = 1232.8(2) pm. The anionic part of the structure is built up by chains of edge connected [NdCl_4/2Cl₂(H₂O)₂]^– trigondodecahedra. In order to study the interactions between the neodymium cation and the ligands magnetic measurements were carried out. The magnetic data were interpreted by ligand field calculations applying the angular overlap model.     

Synthese,Eigenschaften und Struktur von Amin-Addukten der Lithium-tris[bis(trimethylsilyl)methyl]zinkate

Synthesis, Properties, and Structure of the Amine Adducts of Lithium Tris[bis(trimethylsilyl)methyl]zincates . Bis[bis(trimethylsilyl)methyl]zinc and the aliphatic amine 1,3,5-trimethyl-1,3,5-triazinane (tmta) yield in n-pentane the 1:1 adduct, the tmta molecule bonds as an unidentate ligand to the zinc atom. Bis[bis(trimethylsilyl)methyl]zinc · tmta crystallizes in the triclinic space group P1 with {a = 897.7(3); b = 1 114.4(4); c = 1 627.6(6) pm; α = 90.52(1); β = 103.26(1); γ = 102.09(1)°; Z = 2}. The central C₂ZnN moiety displays a nearly T-shaped configuration with a CZnC angle of 157° and Zn? C bond lengths of 199 pm. The Zn? N distances of 239 pm are remarkably long and resemble the loose coordination of this amine; a nearly complete dissociation of this complex is also observed in benzene. The addition of aliphatic amines such as tmta or tmeda to an equimolar etheral solution of lithium bis(trimethylsilyl)methanide and bis[bis(trimethylsilyl)methyl]zinc leads to the formation of the amine adducts of lithium tris[bis(trimethylsilyl)methyl]zincate. Lithium tris[bis(trimethylsilyl)methyl]zincate · tmeda · 2 Et₂O crystallizes in the orthorhombic space group Pbca with {a = 1 920.2(4); b = 2 243.7(5); c = 2 390.9(5) pm; Z = 8}. In the solid state solvent separated ions are observed; the lithium cation is distorted tetrahedrally surrounded by the two nitrogen atoms of the tmeda ligand and the oxygen atoms of both the diethylether molecules. The zinc atom is trigonal planar coordinated; the long Zn? C bonds with a value of 209 pm can be attributed to the steric and electrostatic repulsion of the three carbanionic bis(trimethylsilyl)methyl substituents.     

Gestrecktkettige Kristalle von POM-Copolymeren: Synthese, Struktur und Eigenschaften

Ohne Zusammenfassung     

Die Synthese und einige Eigenschaften von Hydraziniumfluoroscandaten(III)

The synthesis of N₂H₅ScF₄·0.5 HF·0.5 H₂O, N₂H₅ScF₄, and N₂H₆ScF₅ is described. The thermal properties and infrared spectra of the compounds obtained are discussed. The assignation of the bands in infrared spectra (4000 to 250 cm^?1) of the first two compounds is consistent with the presence of hydrazinium⁺¹ ion and for the third one with the presence of hydrazinium⁺² ion.     

Zur Reaktion der Lanthanoiden mit Chelatliganden Darstellung und Struktur von [(py2CH)3Gd]

On the Reaction of the Lanthanides with Chelate Ligands Synthesis and Crystal Structure of [(py₂CH)₃Gd] GdBr₃ reacts with [(py₂CH)Li] to the mononuclear complex [(py₂CH)₃Gd] 1 . The structure of 1 was characterized by X-ray single crystal structure analysis. Space group P2₁, Z = 2, a = 951.4(10) pm, b = 1369.4(10) pm, c = 1074.5(10) pm, β = 105.69(8)°. The Gd-Ion is surrounded by the six nitrogen atoms of the three chelate ligands and shows a distorted trigonal prismatic coordination. As a difference to the lithium salt of the ligand, the six-membered metalla-cycles in 1 are not planar, but show a boat conformation.     

Synthese und Struktur von Silber(II)-tetrafluoroaurat(III) Ag[AuF4]2

Synthesis and Structure of Silver(II) Tetrafluoroaurate(III) Ag[AuF₄]₂ Intensive green single crystals of Ag[AuF₄]₂ can be obtained by heating up micro crystalline Ag[AuF₄]₂ in autoclaves (p(F₂) ～ 200 bar, T ～ 400°C, t ～ 14 d). It crystallizes monoclinic, space group P2₁/n ? C; (No. 14) with a = 522.3(1), b = 1101.3(3), c = 550.5(2) pm, β = 94.98(3), Z = 2 and is isotypic with Pd[AuF₄]₂.     

Synthese und Struktur von [(Ph3C6H2)Te]2, [(Ph3C6H2)Te(AuPPh3)2]PF6 und [(Ph3C6H2)TeAuI2]2

Synthesis and Structure of [(Ph₃C₆H₂)Te]₂, [(Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ and [(Ph₃C₆H₂)TeAuI₂]₂ [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with Ph₃PAu⁺ to yield [2,4,6-Ph₃C₆H₂TeAuPPh₃₂]PF₆ which can be oxidized by I₂ to form the gold(III) complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂. [(2,4,6-Ph₃C₆H₂)Te]₂ crystallizes in the monoclinic space group P2₁/c with a = 810.6(2); b = 2026.5(5); c = 2260.6(7) pm; β = 99.23(3)° and Z = 4. In the crystal structure the ditelluride exhibits a dihedral angle C11? Te1? Te2? C21 of 66.1(2)°. The distance Te1? Te2 is 269.45(6) pm. In the cation of the triclinic complex [(2,4,6-Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ (space group P1 ; a = 1197.4(3); b = 1457.2(4); c = 1680.0(6) pm; α = 84.69(3)°; β = 85.11(3)°; γ = 75.54(3)°; Z = 2) a pyramidal skeleton RTeAu₂ with distances Te? Au = 259.2(1) and 257.8(2) pm and Au? Au = 295.3(1) pm is present. [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ crystallizes in the triclinic space group P1 with a = 1086.3(3); b = 1462.9(6); c = 1654.2(2) pm; α = 85.25(2)°; β = 87.44(1)°; γ = 80.90(3)°; Z = 2. In the centrosymmetrical dinuclear complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ the Au atoms exhibit a square-planar coordination by two iodine atoms and two tellurolate ligands. The tellurolate ligands form symmetrical bridges with distances Te? Au = 260.0 pm. The distances Au? I are in the range of 260.3(1) and 263.7(1) pm.