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Zur Reaktion von [(η3-C4H7)PdCl]2 mit Se(SiMe3)2. Die Kristallstruktur von [(η3-C4H7)6Pd6Se3]
(1988)
[(η3-C4H7)PdCl]2 reacts with Se(SiMe3)2 to form [(η3-C4H7)6Pd6Se3] (1). 1 has been characterized by X-ray crystal structure analysis. It contains a distorted trigonal prismatic Pd6-cluster. Three faces of the Pd-prism are occupied by μ4-Se ligands. 1 crystallizes in the space group Pnma with 4 formula units per unit cell. The lattice constants at 200 K are: a = 1175.1(8), b = 1611.4(12), c = 1720.3(12) pm.
[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.
(η5-C5H5)Fe(CO)2Br reacts with Se(SiMe3)2 to form the title compound 1, which has been characterized by X-ray crystal structural analysis. 1 crystallizes in the space group P212121 with 4 formula units per unit cell. 1 consists of [Se{Fe(CO)2(C5H 5)}3]+- cations and [Fe4Se4Br4]2--anions, the latter with a heterocubane structure.
(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.
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.
WCl4(NCl) has been prepared as a red-brown crystal powder by the reaction of tungsten hexacarbonyl with excess nitrogen trichloride in boiling CCl4. The complex is associated via chloro bridges, forming dimeric units, according to the IR spectrum. Thermal decomposition at 200 °C leads to tungsten nitride trichloride, WNCl3,. With acetonitrile, WCl4(NCl) reacts with formation of the monomeric complex [CH,CN-WCl4(NCl)], which was characterized by its IR spectrum as well as by an X-ray structure determination. Crystal data: space group P21/m, Z = 2 (1387 independent observed reflexions, R = 0.07). Lattice dimensions at 20 °C: a = 590.4(3), b = 729.0(3), c = 1124.6(4) pm, β = 100.63(2)°. The complex forms monomeric molecules, in which the tungsten atom has a distorted octahedral environment of four chlorine atoms in equatorial positions, and the acetonitrile molecule in trans-position to the group. Bond lengths WN = 172 and NCI = 161 pm; bond angle WNCl = 175.5°.
The reaction of [Cp2TiCl2 ] with E(SiMe3)2 leads to dinuclear Ti complexes. In [Cp3Ti2S2Cl] (1) and [Cp3Ti2Se2Cl] (3) two μ2 -S(Se) ligands bridge the Cp2Ti and CpTiCl units, respectively in contrast to these, [Cp4Ti2S2Cl2] (2) contains a μ2η1-S2 bridge connecting two Cp2TiCl fragments. A similar reaction of [CpTiCl3] with Se(SiMe3)2 leads to the tetranuclear cluster [Cp4Ti4Se7O] (4). 4 consists of a Ti4 -tetrahedron which encloses an oxygen atom.