Refine
Document Type
- Article (21)
Language
- German (21)
Has Fulltext
- yes (21)
Is part of the Bibliography
- no (21)
Keywords
- Synthesis (14)
- Crystal Structure (13)
- IR Spectra (10)
- X-Ray (7)
- Acetonitrile Adduct (2)
- 1,1-dichloro-3,5-diphenyl-4-H-1,2,4,6-λ4-selenatriazine (1)
- 19F NM R Spectra (1)
- Bis(η-cyclopentadienyl)titana(TiIV)cyclohexaselenane (1)
- Copper(I) Chloride Adducts of Phosphoranimines (1)
- Crystal Structure Dinuclear Ti-S and Ti-Se Complexes (1)
Institute
- Biochemie und Chemie (21)
[Ph3PN(H)Ph][AuI2] (2) is formed by the reaction of AuI with N-Phenyl-iminotriphenylphosphorane, Ph3PNPh in a toluene suspension. 2,3-Bis(triphenylphosphinimino)maleic acid-N-methylimide (3) has been prepared by the Staudinger reaction of 2,3-bis(azido)maleic acid-N-methylimide with PPh3 in THF solution in the form of red crystals. Crystal structure determinations of three iminophosphoranes were carried out by X-ray methods.
Ph3PNPh (1): space group P21/c, Z = 4, 2176 independent observed reflexions, R = 0.057. Lattice dimensions (-30 °C): a = 1126.4, b = 1148.6, c = 1476.0 pm; β = 97.21°. The compound forms monomeric molecules with P=N = 160.2 pm and an PNC angle of 130.4°.
[Ph3PN(H)Ph][AuI2] (2): space group P1̄, Z = 2, 1780 independent observed reflexions, R = 0.057. Lattice dimensions (18 °C); a = 824.9, b = 1022, c = 1476.2 pm; α = 89.23°, β = 87.41°, γ = 85.65°. The compound consists of ions [Ph3PN(H)Ph]⊕ with P=N = 162.4 pm and PNC = 129.3°, and anions [AuI2]⊖ with Au-I = 261.9 and 259.3 pm, IAuI = 176.8°.
(Ph3P)2N2C4O2 (NMe) (3): space group P1̄, Z = 2, 4972 independent observed reflexions, R = 0.050. Lattice dimensions (-90 °C): a = 904.7, b = 993.8, c = 2017.4 pm; α = 101.55°, β = 96.39°, γ = 105.81°. The compound forms monomeric molecules with syn-conformation of the two NPPh3 groups. Bond lengths: P=N = 157.1; 155.3 pm, bond angles: PNC = 133°; 136°.
(NBu4)2[Co4(SPh)6Cl4] (1) and [Co4(SPh)6CU(PPh3)2] (2) are prepared by the reaction of (NBu4)[CoCl3(PPh3)] and [CoCl2(PPh3)2] with PhSSiMe3 in toluene solution. The overall description of the Co4S6Cl4 core is that o f a nearly regular Co4-tetrahedron inscribed in an irregular octahedron of the bridging S atoms resulting in an “adamantane” type cage. 1 reacts with Na[Mn(CO)5] to form the dinuclear complex (NBu4)[Mn2(SPh)3(CO)6] (4). Each Mn atom is bound to three CO and three μ2-SPh ligands. The Mn-Mn contact (318.5 pm) does not indicate metal-metal bonding.
Cp2TiSe5 has been prepared by the reaction of trim ethyltetradecylammonium-polyselenide with Cp2TiCl2 in ethanol solution and subsequent extraction of the dry residue with dichloromethane. Cp2TiSe5 crystallizes in the space group P1 with two formula units in the unit cell (2559 observed, independent reflexions, R = 0.074). The cell dimensions are a = 808.6, b = 822.6, c = 1190.7 pm, α - 96.28°, β - 106.06°, γ = 108.78°. The structure consists of discrete Cp2TiSe5 molecules with the TiSe5, ring in the chair conformation.
The title compound has been prepared from (PPh4)2[Mo2(O2C-Ph)4Cl2] and CCl4 in CH2Cl2 solution as moisture sensitive crystals, which are black in reflexion and yellow in transmission. (PPh4)2[Mo2(O2C-Ph)4Cl4] · 2 CH2Cl2 was characterized by a X-ray crystal structure determination (7873 observed independent reflexions. R = 0.048). It crystallizes in the space group P1̄ with one formula unit in the unit cell; the lattice constants are a = 1186.4; b = 1404.0; c = 1451.0 pm; α = 61.98°; β = 78.91°; γ = 78.26°. The structure consists of PPh4⊕ ions. CH2Cl2 molecules and centrosymmetric anions [Mo2(O2C-Ph)4Cl4]2⊝ containinga molybdenum d3 d3 unit with a relatively long Mo=Mo bond of 249.6 pm. The Mo≡Mo group is spanned in a chelate manner by four O atoms of two benzoate groups and by two further single O atoms of two further benzoate groups. Two terminal Cl atoms on each Mo atom complete the pentagonal bipyramidal coordination spheres about the Mo atoms.
MoF4(NCl) has been prepared as a yellow crystal powder by the reaction of diluted fluorine with MoCl3(N3S2) at room temperature. The compound is associated via fluorine bridges, according to the IR spectrum. With acetonitrile, the monomeric complex [CH3CN -MoF4(NCl)] is obtained, which was characterized by its IR and 19F NMR spectra as well as by an X-ray structure determination. Crystal data: space group Pm, Z = 2 (1068 observed, independent reflexions, R = 0.03). Lattice dimensions at -90 °C: a = 507.1. b = 704.8, c = 995.8 pm, β = 102.02°. The unit cell contains two crystallographically independent molecules [CH3CN -MoF4(NCl)], the Mo≡N-Cl groups being linear (bond angles 176°, 178°) with bond lengths MoN = 172 and NCI = 159, 162 pm. In the trans position to the MoNCl group, the nitrogen atom of the acetonitrile molecule is coordinated.
[η5-CpMCl4] (M = Nb, Ta) reacts with E(SiMe3)2 (E = S, Se) to form different multinuclear clusters. The cation [Cp8Ta6S10]2+ (1) consists of a planar Ta2S2-ring of which each Ta is coordi-nated to two Cp2TaS2-fragments. [Cp4Ta4S13] (3) can be derived from [Cp3Ta3S7Cl2] (2) by addition of a CpTaS6-unit to a triangle of Ta-atoms bridged by S- and S2-ligands. The niobium atoms in [Cp3Nb3Se5Cl2] (4) arrange in a chain structure with Nb coordination numbers varying from 4-6.
The title compound has been prepared by the reaction of N,N,N′-tris(trimethylsilyl)benzamidine with tantalum pentachloride in CH2Cl2 suspension, forming amber-coloured, moisturesensitive crystals, which were characterized by an X-ray structure determination. Space group P 21/n, Z = 2, 4895 observed independent reflexions, R = 0.059. Lattice dimensions (-65°C): a = 1165.2(6), b = 1335.4(6), c = 1629.0(7) pm, β = 93.23(4)°. The complex forms centrosymmetric molecules dimerized via chloro bridges TaCl2Ta with TaCl bond lengths of 247.2(2) and 277.1(2) pm, the longer one being in trans-position to the imido group, which can be formulated as [xxx] (bond lengths Ta=Ν = 183.5(8), C=N = 134(1) pm, bond angle TaNC = 162.7(7)°).
(NBu4)[CoCl3(PPh3)] reacts with Se(SiMe3)2 to form the new clusters [Co8Se8(PPh3)6][CoCl3(PPh3)] (6) and [Co8Se8(PPh3)6][Co6Se8(PPh3)6] (7). The structures of 6 and 7 have been determ ined by X-ray diffraction. 6 and 7 crystallize in the space group P1̄ with two formula units per unit cell and with the following lattice constants at 180 K: 6: a = 1413.8(10), b - 2224.2(23), c = 2348.4(17) pm, α = 86.06(5), β = 86.58(5), γ = 76.11(5)°; 7: a = 1465.9(4), b = 1627.6(6), c = 2505.7(6) pm, α - 98.69(2), β = 96.23(2), γ = 113.06(2)°. The cluster structures of the [Co8Se8(PPh3)6]n (n = 0, 1 +) depend on the total number of electrons in the cluster units.
Kristallstruktur von 1,1-Dichlor-3,5-diphenyl-4-H-1,2,4,6-λ4-selenatriazin, SeCl2C2N3H(C6H5)2
(1989)
The title compound has been prepared as a byproduct of the reaction of Se2Cl2 with Ν,Ν,N′-Tris(trimethylsilyl)benzamidine in CH2Cl2 solution. [SeCl2(HNC2N2Ph2)]2 was characterized by an X-ray structure determination. Space group P21/n, Z = 2, 2979 observed independent reflexions, R = 0.032. Lattice dimensions (-65 °C): a = 1050.1(4), b = 1018.9(4), c = 1402.1(6) pm; β = 99.78(3)°. The compound forms centrosymmetric dimeric molecules with SeCl2Se bridges (bond lengths 241.6(1) and 339.3(1) pm), the selenium atoms being members of nearly planar [xxx] selenatriazine rings with Se—N bond lengths of 182.2(2) and 181.5(2) pm.
W2NCl7 has been prepared by the reaction of tungsten pentachloride with the bromide of Millon's base, [Hg2N]Br, in boiling CCl4. The product forms a dark brown, moisture sensitive crystal powder (μeff = 0.7 B.M. at 21 °C). With phosphoryl chloride, the complex W2NCl7·2 POCl3 is formed. The reaction with chlorine leads to the mixed-valenced W(V)/W(VI) complex W2NCl8 (μeff = 0.5 B.M. at 22 °C), which reacts with tetraphenylphosphonium chloride in CH2Cl2 to form (PPh4)2[W2NCl10] ·2CH2Cl2. The reactions of W2NCl7 with PPh4Cl in molar ratios in CH2Cl2 solution lead to several complexes; one of them was identified bv X-ray diffraction methods to be (PPh4)2[W3Cl9(μ3-N)(0)(μ2-NCl)]2 ·1,5 CH2Cl2, which forms black crystals. The compound crystallizes monoclinically in the space group P21/n with two formula units per unit cell (7318 observed, independent reflexions, R = 0.083). The lattice dimensions are (20 °C): a = 994.4; b = 2673; c = 1518.2 pm; β = 101.00°. The compound consists of PPh4⊕ cations and centrosymmetric anions [W3Cl9(μ3-N)(O)(μ2-NCl)]22⊕. The tungsten atoms form a scalene triangle with WW bond lengths of 282 and 278 pm, respectively. The hypothenuse of this triangle is a nearly linear W - N -W bridge with WN distances of 199 and 182 pm. One of the WW edges is bridged by a μ-NCI group with WN bond lengths of 196 und 189 pm. respectively.