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1.
PPh4[As3S3Cl4] and PPh4[As3S3Br4] When As2S3 reacts with PPh4X and HX in 1,2-C2H4X2 (X = Cl, Br), the title compounds are obtained as minor products; the main products are PPh4[As2SX5]. Their crystal structures were determined by X-ray diffraction. PPh4[As3S3Cl4]: a = 1187.7, b = 1090.9, c = 1191.8 pm, α = 82.91, β = 88,93, γ = 88.52°; twins with twin plane (100); R = 0.109 for 1618 observed reflexions of one twin crystal. PPh4[As3S3Br4]: a = 1119.7, b = 1177.5, c = 1204.1 pm, α = 81.59, β = 85.88, γ = 88.25°; R = 0.061 for 2331 observed reflexions. Both compounds crystallize in the space group P1 , Z = 2, and can be considered to be isotypic. Nevertheless, PPh4[As3S3Br4] does not form twins as PPh4[As3S3Cl4]. The crystals consist of PPh4+ and [As3S3X4]? ions. In the anions, the three As atoms of an As3S3 ring in the chair conformation are commonly joined to an X atom and each As atom is bonded to one further terminal X atom. Cations and anions are packed in alternating layers. 相似文献
2.
Thiochloroarsenates (III): Preparation, Vibrational Spectra, and Crystal Structures of PPh4[As2SCl5] and (PPh4)2[As2SCl6] · C2H4Cl2 PPh4[As2SCl5] can be obtained from As2S3 + PPh4Cl with HCl in CH2Cl2 or 1,2-C2H4Cl2. It reacts with a second mole of PPh4Cl to yield (PPh4)2[As2SCl6]. The latter also is formed by the reaction of As2S5 + 2 PPh4Cl with HCl, a second product being (PPh4)2[As2Cl8]. The i.r. and Raman spectra of the title compounds are reported. Their crystal structures were determined by X-ray diffraction. Crystal data: PPh4[As2SCl5], monoclinic, space group P21/n, a = 1175.8, b = 1508.0, c = 1593.4 pm, β = 96.22°, Z = 4; (PPh4)2[As2SCl6] · C2H4Cl2, triclinic, P1, a = 1166.3, b = 1188.2, c = 2044.6 pm, α = 95.47, β = 97.53, γ = 111.05°, Z = 2. Including the lone electron pairs, the coordination of the As atoms in the [As2SCl5]− ion is distorted trigonal-bipyramidal with the S, one Cl atom, and an electron pair in equatorial positions; the two bipyramids around the two As atoms share a common edge. The As atoms in the [As2SCl6]2− ion have a distorted octahedral coordination, the two octahedra share a common face; the lone electron pairs are in the trans positions to the S atom. 相似文献
3.
Novel Routes to the Synthesis of Thiohalogeno- and Cyclothioarsenates(III). Crystal Structures of PPh4[As2SBr6] · CH3CN and PPh4[SAsS5] By reactions of (PPh4)2[As2Cl8] and (PPh4)2[As2Br8] with Na2S4 in acetonitrile (PPh4)2[As2SCl6] · CH3CN and (PPh4)2[As2SBr6] · CH3CN were obtained, respectively. Using K2S5, PPh4[As2SCl5] and PPh4[SAsS5] were the products. The latter can also be obtained from PPh4[As2SCl5] and Na2S4, while PPh4[As3S3Br4] is formed from PPh4[As2SBr5] with K2S5. Two X-ray crystal structure determinations were performed. PPh4[As2SBr6] · CH3CN: triclinic, P1 , Z = 2, a = 1200.4(7), b = 1507.3(6), c = 1594.4(8) pm, α = 81.59(2), β = 78.22(3), γ = 80.58(2)°, R = 0.096 for 2298 observed reflexions. The structure contains [As2SBr6]2? -ions in which the two Sb atoms are joined via one S and two Br atoms. PPh4[SAsS5]: triclinic, P1 , Z = 2, a = 1133.9(4), b = 1142.5(4), c = 1186.9(5) pm, α = 102.77(4), β = 107.74(3), γ = 106.65(3)°, R = 0.043 für 2677 reflexions. In the [SAsS5]? -ion an AsS5 ring in the chair conformation is present. 相似文献
4.
Pentabromothio-diarsenate and -diantimonate: Preparation, Vibrational Spectra, and Crystal Structures of PPh4[As2SBr5] and PPh4[Sb2SBr5] The title compounds were obtained in CH2Br2 from PPh4Br, HBr and As2S3 or Sb2S3, respectively. Their i.r. and Raman spectra are reported. Their crystal structures were determined by X-ray diffraction. Crystal data: PPh4[As2SBr5], monoclinic, space group P21/n, Z = 4, a = 1192.3, b = 1528.1, c = 1618.0 pm, β = 95.53°, isotypic with PPh4[As2SCl5] (structure determination with 1539 observed reflexions, R = 0.052); PPh4[Sb2SBr5], triclinic, space group P1 , Z = 2, a = 1044,8, b = 1207.1, c = 1307.8 pm, α = 104.77, β = 108.63, γ = 98.34° (2398 observed reflexions, R = 0.032). Both ions, [As2SBr5]? and [Sb2SBr5]?, have the same general structure: including the lone electron pairs, the As and Sb atoms have distorted trigonal-bipyrimidal coordination, two bipyramids sharing a common edge with sulfur and bromine as bridging atoms. The [As2SBr5]? ions are associated to chains via As…Br contacts, the [Sb2SBr5]? ions form pseudodimeric units by Sb…S and Sb…Br contacts. Whereas the crystal packing of the As compound is similar to that of other PPh4+ compounds having a cation to anion ratio of 1:1, the Sb compound shows the packing principle known for 2:1 compounds. 相似文献
5.
Formation of PPh4[WOCl4 · THF] and PPh4Cl · 4As4S3 from W(CO)6 and PPh4[As2SCl5] and their Crystal Structures When W(CO)6 and PPh4[As2SCl5] are irradiated with UV light in tetrahydrofurane, PPh4[WOCl4 · THF], PPh4 Cl· 4As4S3 and PPh4[Cl2H] are obtained. X-ray crystal structure determinations were performed. PPh4[WOCl4 · THF], monoclinic, space group P21/c, Z = 4, a = 1207.5(2), b = 1003.7(2), c = 2642.0(5) pm, β = 114.71(1)°, R = 0.049% for 2824 reflexions; PPh4+ and [WOCl4. THF]? ions are present, the WOCl4 group having the shape of a tetragonal Pyramid with a short W ? O bond (169 pm) and the THF molecule being weakly associated (W? O 236 pm). PPh4Cl · 4AsS3, tetragonal, I41/a, Z = 4, a = 1742.3(3), c = 1664.5(4) pm, R = 0.066% for 1350 reflexions; it consists of separate PPh4+ and Cl? ions and As4S3 molecules. 相似文献
6.
Thiobromo Complexes of Arsenic and Antimony. Preparation and Crystal Structures of (PPh4)2[As2SBr6] · CH2Br2 and (PPh4)2[Sb2SBr6] · CH2Br2 (PPh4)2[As2SBr6] · CH2Br2 is formed by the reaction of As2S3, PPh4I and HI in dibromomethane. It can also be obtained, as well as (PPh4)2[Sb2SBr6] · CH2Br2, from (PPh4)2[As2Br8] and (PPh4)3[Sb2Br9], respectively, with bistrimethylsilylsulfide. The crystal structures of the title compounds were determined by X-ray diffraction. They are isotypic with (PPh4)2[As2SCl6] · C2H4Cl2. In the anions [M2SBr6]2? the M atoms (As or Sb) have a distorted octahedral coordination, the two octahedra share acommon face with one bridging S and two Br atoms; the lone electron pairs occupy the trans positions to the S atom. Crystal data: triclinic, space group P1 , Z = 2; (PPh4)2[As2SBr6] · CH2Br2, a = 119.1, b = 1203.6, c = 2067.5 pm α= 94.89, β = 97.78, γ = 112.20°, 3046 independent observed reflexions, R = 0.083; (PPh4)2[Sb2SBr6] · CH2Br2, a = 1198.9, b = 1224.3, c = 2085.5pm, α = 95.04, β = 98.48, γ = 112.13°C, 2380 reflexions, R = 0.079. 相似文献
7.
Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh4[Sb2SCl5] and (PPh4)2[Sb2SCl6]. CH3CN (PPh4)2Sb3Cl11, obtained from Sb2S3, PPh4Cl and HCl, reacts with Na2S4 in acetonitrile forming PPh4[Sb2SCl5]. From this and Na2S4 or from (PPh4)2[Sb2Cl8] and Na2S4 or K2S5 in acetonitrile (PPh4)2[Sb2SCl6] · CH3CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh4[Sb2SCl5], monoclinic, space group P21/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh4)2[Sb2SCl6] · CH3CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl5]? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting. 相似文献
8.
The Chlorooxoarsenates(III) (PPh4)2[As4O2Cl10] · 2 CH3CN and (PPh4)2[As2OCl6] · 3 CH3CN (PPh4)2[As2Cl8] can be prepared from As2O3, SOCl2 and PPh4Cl in acetonitrile. Its oxidation with chlorine yields PPh4[AsCl6]. This was also obtained directly from arsenic, chlorine and PPh4Cl, (PPh4)2[As4O2Cl10] · 2 CH3CN being a side product; the latter was obtained with high yield from AsCl3, As2O3 and PPh4Cl in acetonitrile. By addition of PPh4Cl it was converted to (PPh4)2[As2OCl6] · 3 CH3CN. According to their X-ray crystal structure analyses, both crystallize in the triclinic space group P 1. The [As4O2Cl10]2– ion can be regarded as a centrosymmetric association product of two Cl2AsOAsCl2 molecules and two Cl– ions, each Cl– ion being coordinated with all four As atoms. In the [As2OCl6]2– ion the As atoms are linked via the O atom and two Cl atoms. 相似文献
9.
Cyclic Polyselenidoarsenates(III) and Polyselenidoantimonates(III): PPh4[Se5AsSe], PPh4[AsSe6–xS x ], (PPh4)2[As2Se6] · 2 CH3CN, and (PPh4)2[Se6SbSe]2 In acetonitrile, AsCl3 and sodiumphenolate formed Cl2AsOPh which then was reacted with PPh4Se5 and finally with Na2Se to yield PPh4[Se5AsSe]. With Na2S instead of Na2Se, PPh4[AsSe6–xSx] was obtained; the sulfur contents increased with increasing reaction temperature and time (x = 0.21 to 1.09). With PPh4Se2 instead of PPh4Se5, (PPh4)2[1,4-As2Se6] · 2 CH3CN and PPh4[Se5AsSe] were the products. With SbCl3 instead of AsCl3, (PPh4)2[Se6SbSe]2 formed. PPh4[Se5AsSe] can also be produced from As2Se3, PPh4Br, Na2Se and selenium in acetonitrile. The crystal structure of PPh4[SeAsSe5] is isotypic with PPh4[S5AsS] (X-ray structure analysis with 2414 observed reflexions, R = 0.038). The Se5AsSe– ion consists of a six-membered AsSe5 ring in chair conformation, and the As atom has an additional terminal Se atom. The compounds PPh4[AsSe6–xSx] have the same crystal structures, with sulfur atoms taking all selenium positions at random, but with a preference for the terminal position. The anion in (PPh4)2[As2Se6] · 2 CH3CN also has a six-membered ring structure in chair conformation, with two arsenic atoms in positions 1 and 4. The centrosymmetric anion in (PPh4)2[Se6SbSe]2 consists of a central Sb2Se2 ring, and a Se6 ligand is bonded in a chelating manner to each Sb atom (X-ray structure analysis with 2669 observed reflexions, R = 0.099). 77Se-NMR spectra are reported. 相似文献
10.
Azido Complexes of Manganese(II) and Cobalt(II). Crystal Structures of (PPh4)2[Mn(N3)4] and PPh42[Co(N3)3Cl] (PPh4)2[Mn(N3)4] and (PPh4)2[Co(N3)3Cl] were obtained as light-brown and green blue, nonexplosive crystalline compounds, respectively. They are only slightly sensitive to moisture and were obtained from the tetrachloro complexes (PPh4)2MCl4 by reactions with silver azide in dichloromethane. The compounds were characterized by thier i.r. spectra and by crystal structure analyses. Both crystallized in the monoclinic space group C2/c, Z = 4, but they are not isotypic. (PPh4)2[Mn(N3)4]: structure determination with 711 independent reflexions, R = 0.097; a = 2249.1, b = 1499.6, c = 1370.3 pm, β = 104.86°. (PPh4)2[Co(N3)Cl]: 2753 reflexions, R = 0.075; a = 1119.7, b = 1899.2, c = 2115.4 pm, β = 90.47°. The structures consist of PPh4+ ions and of anions that are situated on twofold crystallographic rotation axes. The anions show positional disorder, statistically assuming two different orientations with probabilities of 50% each; in the case of [Co(N3)3Cl]2?, the Cl atom is superimposed statistically with an azido group, whereas the [Mn(N3)4]2? ion is tilted by about 20° from the ideal position to two sides of the crystallographic axis. In both compounds the cation form layers and the anions are located between the layers. 相似文献
11.
Mono- and Binuclear Dinitrosyl Complexes of Molybdenum and Tungsten. Crystal Structures of (PPh3Me)2[WCl4(NO)2], (PPh3Me)2[MoCl3(NO)2]2, and (PPh3Me)2[WCl3(NO)2]2 The complexes (PPh3Me)2[MCl4(NO)2] (M = Mo, W), and (PPh3Me)2[MCl3(NO)2]2, respectively, are prepared by reactions of the polymeric compounds MCl2(NO)2 with triphenylmethylphosphonium chloride in CH2Cl2, forming green crystals. According to the IR spectra the nitrosyl groups are in cis-position in all cases. The tungsten compounds as well as (PPh3Me)2[MoCl3(NO)2]2 were characterized by structure determinations with X-ray methods. (PPh3Me)2[WCl4(NO)2]: space group C2/c, Z = 4. a = 1874, b = 1046, c = 2263 pm, β = 119.99°. Structure determination with 3492 independent reflexions, R = 0.057. The compound consists of PPh3Me⊕ ions, and anions [WCl4(NO)2]2? with the nitrosyl groups in cis-position (symmetry C2v). (PPh3Me)2[WCl3(NO)2]2: Space group C2/c, Z = 4. Structure determination with 2947 independent reflexions, R = 0.059. (PPH3Me)2[MoCl3(NO)2]2: Space group P1 , Z = 1. a = 989, b = 1134, c = 1186 pm; α = 63.25°, β = 80.69°, γ = 69.94°. Structure determination with 3326 independent reflexions, R = 0.046. The compounds consist of PPh3Me⊕ ions, and centrosymmetric anions [MCl3(NO)2]22?, in which the metal atoms are associated via MCl2M bridges of slightly different lengths. One of the NO groups is in an axial position, the other one in equatorial position (symmetry C2h). 相似文献
12.
Syntheses and Crystal Structures of the Polytellurido Complexes (PPh4)4[M2Te12] of Copper(I) and Silver(I) The title compounds have been prepared as black crystal needles by reactions of Na2Te3 with CuCl and AgNO3, respectively, in dimethylformamide in the presence of PPh4Br. With regard to the large cell dimensions the crystal structure determinations were done by an imaging plate instrument. (PPh4)4[Cu2Te12]: Space group P21/n, Z = 6, 51 338 detected reflections, structure determination with 14 177 unique reflections with I > 4σ(I), R = 0.081. Lattice dimensions at ? 50°C: a = 1 704.5, b = 1 694.5, c = 5 044 pm, β = 94.20°. (PPh4)4[Ag2Te12]: Space group P21/n, Z = 6, 80 811 detected reflections, structure determination with 16 092 unique reflections with I > 3σ(I), R = 0.052. Lattice dimensions at ? 50°C: a = 1 703.8, b = 1 722.9, c = 5 123 pm, β = 94.65°. The structures of the isotypic compounds consist of six symmetry independent PPh4+ ions and two symmetry independent anions [M2Te12]4?, in which the metal atoms of two (MTe4)?-fivering fragments are linked by a Te42? chain. 相似文献
13.
The Crystal Packings of (PPh4)2[NiCl4] · 2 MeCN and PPh4[CoCl0.6Br2.4(NCMe)] (PPh4)2[NiCl4] · 2 MeCN was obtained from the reaction of PPh4Cl and NiCl2 in acetonitrile in the presence of S2Cl2, PPh4[Cl2H] being a side product. The product of the reaction of CoS2 with S2Br2 (containing rests of S2Cl2) at 400 °C was treated with PPh4Br in acetonitrile yielding PPh4Br3 and PPh4[CoCl0.6Br2.4(NCMe)]. The crystal structures of the title compounds were determined by X‐ray diffraction. (PPh4)2[NiCl4] · 2 MeCN (space group I 4, a = 1839.3 pm, c = 1375.3 pm) has a crystal packing derived from the BiPh4[ClO4] structure type with a fourfold increased unit cell and one half of the ClO4– positions substituted by pairsof acetonitrile molecules. The crystal structure of PPh4[CoCl0.6Br2.4(NCMe)] (space group I41/a, a = 1804.7 pm, c = 3198.8 pm) is related to the AsPh4[RuNCl4] type with an eightfold increased unit cell. The [CoCl0.6Br2.4(NCMe)]– ions are disordered in two orientations and some halogen positions are randomly occupied by Cl and Br atoms. Family trees of group–subgroup relations show the symmetry relations. 相似文献
14.
Tetraphenylphosphonium Heptathiacyclo Thioarsenate(III), PPh4[SAsS7] From PPh4[As2SCl5] und K2S5 the title compound was obtained in acetonitrile among other products. According to an X-ray crystal structure analysis, it crystallizes in the orthorhombic space group Pna21 with a = 1 826.1(3), b = 1 312.0(2), c = 1 215.9(2) pm, Z = 4. The structure consists of PPh4+ and [SAsS7]? ions, AsS7 rings in the crown conformation as in S8 being present. 相似文献
15.
Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O], and (PPh4)2[SnCl6] · S8 · 2CH3CN . The reaction of PPh4[SnCl3] with Na2S4 in acetonitrile in the presence of small amounts of water yields (PPh4)2[Sn4Cl4S5(S3)O] and minor amounts of (PPh4)2[SnCl2(S6)2], PPh4Cl · 2S8 and (PPh4)2[SnCl6]. SnCl4 is partially reduced by (PPh4)2Sx, PPh4[SnCl3] and (PPh4)2[SnCl6] · S8 · 2CH3CN being produced. According to the X-ray crystal structure determination the [Sn4Cl4S5(S3)O]2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S3 group. In the [SnCl2(S6)2]2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S6 groups. Octahedral [SnCl6]2? ions and S8 molecules in the crown conformation are present in (PPh4)4[SnCl6] · S8 · 2CH3CN. 相似文献
16.
Synthesis and Crystal Structures of (PPh4)2[TeS3] · 2 CH3CN and (PPh4)2[Te(S5)2] (PPh4)2[TeS3] · 2 CH3CN was obtained by the reaction of PPh4Cl, Na2S4 and Te in acetonitrile. With sulfur it reacts yielding (PPh4)2[Te(S5)2]. The crystal structures of both products were determined by X-ray diffraction. (PPh4)2[TeS3] · 2 CH3CN: triclinic, space group P1 , Z = 2, R = 0.041 for 4 629 reflexions; it contains trigonal-pyramidal [TeS3]2? ions with an average Te? S bond length of 233 pm. (PPh3)2[Te(S5)2]: monoclinic, P21/n, Z = 2, R = 0.037 for 2 341 reflexions. In the [Te(S5)2]2? ion the tellurium atom has a nearly square coordination by four S atoms. Along with the Te atoms each of the two S5 groups forms a ring with chair conformation. 相似文献
17.
SeBr3[AlBr4] and TeI3[AlI4] – two further Compounds in the SCl3[AlCl4] Structure Type The reaction of SeBr4 and AlBr3 in a closed glass ampoule at 150°C yields quantitatively SeBr3[AlBr4] in form of yellow moisture sensitive crystals. From Te, two equivalents of I2, and AlI3 one obtains TeI3[AlI4] in form of dark red, moisture sensitive crystals. Both compounds crystallize monoclinic in the space group Pc (SeBr3[AlBr4]: a = 670.7(7) pm, b = 663.9(5) pm, c = 1 428.6(2) pm, β = 101.21(9)°, TeI3[AlI4]: a = 731.9(1) pm, b = 730.8(1) pm, c = 1 565.5(3) pm, β = 102.01(2)°). They are isotypic and have the SCl3[AlCl4] structure type. The structures are built of tetrahedral AlX4? ions and of pyramidal EX3+ ions (E = S, Se, Te; X = Cl, Br, I). The chalcogen atoms are additionally coordinated by halogen atoms of surrounding AlX4? ions, corresponding to a strongly distorted octahedral coordination EX3+3. 相似文献
18.
Reactions of Uranium Pentabromide. Crystal Structures of PPh4[UBr6], PPh4[UBr6] · 2CCl4, (PPh4)2[UBr6] · 4CH3CN, and (PPh4)2[UO2Br4] · 2CH2Cl2 PPh4[UBr6] and PPh4[UBr6] · 2CCl4 were obtained from UBr5 · CH3CN and tetraphenylphosphonium bromide in dichloromethane, the latter being precipitated by CCl4. Their crystal structures were determined by X-ray diffraction. PPh4[UBr6]: 2101 observed reflexions, R = 0.090, space group C2/c, Z = 4, a = 2315.5, b = 695.0, c = 1805.2 pm, β = 96.38°. PPh4[UBr6] · 2CCl4: 2973 reflexions, R = 0.074, space group P21/c, Z = 4, a = 1111.5, b = 2114.2, c = 1718.7 pm, β = 95.42°. Hydrogen sulfide reduces uranium pentabromide to uranium tetrabromide. Upon evaporation, bromide is evolved from solutions of UBr5 with 1 or more then 3 mol equivalents of acetonitrile in dichlormethane yielding UBr4 · CH3CN and UBr4 · 3CH3CN, respectively. These react with PPh4Br in acetonitrile affording (PPh4)2[UBr6] · 4CH3CN, the crystal structure of which was determined: 2663 reflexions, R = 0.050, space group P21/c, Z = 2, a = 981.8, b = 2010.1, c = 1549.3 pm, β = 98.79°. By reduction of uranium pentabromide with tetraethylammonium hydrogen sulfide in dichloromethane (NEt4)2[U2Br10] was obtained; (PPh4)2[U2Br10] formed from UBr4 and PPh4Br in CH2Cl2. Both compounds are extremely sensitive towards moisture and oxygen. The crystal structure of the oxydation product of the latter compound, (PPh4)2[U02Br4]· 2 CH2Cl2, was determined: 2163 reflexions, R = 0.083, space group C2/c, Z = 4, a = 2006.3, b = 1320.6, c = 2042,5 pm, β = 98.78°. Mean values for the UBr bond lengths in the octahedral anions are 266.2 pm for UBr6-, 276.7 pm for UBr62? and 282.5 pm for UO2Br42? 相似文献
19.
Dieter Fenske Bernhard Czeska Christina Schumacher Roland E. Schmidt Kurt Dehnicke 《无机化学与普通化学杂志》1985,520(1):7-17
Disulfido-Bridged Halo Complexes of Molybdenum (V). Crystal Sructures of (PPh3Me)2 [Cl4Mo (μ-S2)2MoCl4]. 2 CH2Cl2 and (PPh4)2[Br4Mo(μ-S2)2MoBr4]. 3CH2Br2 . Mo(S2)Cl3 is prepared by an improved method; the i.r. spectrum is reported. In dichloro methane solution it reacts with (PPh3Me)Cl forming the complex (PPh3Me)2[Cl4Mo(μ-S2)2MoCl4] · 2 CH2Cl2. The bromo complex (PPh4)2[Br4Mo(μ-S2)2MoBr4] · 3 CH2Br2 is obtained by reaction of MoBr4 with S7NH and subsequent treatment of the reaction mixture with PPh4Br in CH2Br2 solution. Both complexes are characterized by i.r. spectra and structural analyses by X-ray methods. (PPh3Me)2[Cl4Mo(μ-S2)2MoCl4] · 2 CH2Cl2 crystallizes monoclinic in the space group P21/c with two formula units per unit cell (5268 observed independent reflexions, R = 4.0%). The lattice dimensions are: a = 1097 pm, b = 1510 pm, c = 1591 pm, β = 104.4°. (PPh4)2[Br4Mo(μ-S2)2MoBr4] · 3 CH2Br2 crystallizes triclinic in the space group P&1macr; with two formula units per unit cell and the lattice constants a = 1328 pm, b = 1573 pm, c = 1719 pm, α = 95.8°, β = 96.3°, γ = 74.1°. Both compounds are of ionical structure with PPh3Me⊕ and PPh4⊕ cations, respectively, and anions [X4MO(μ-S2)2MoX4]2? very similar to each other. The molybdenum atoms are bridged by two disulfido ligands and are bonded directly with a bond length of 286 pm. The terminal halogen atoms add up to coordination number nine at the molybdenum. 相似文献
20.
Inhaltsübersicht. PPh4{MoNCl3[N(SiMe3)2]} entsteht aus PPh4[MoNCl4] und N,N,N′-Tris-(trimethylsilyl)benzamidin in siedendem Dichlormethan in Form bernsteinfarbener Kristalle, die wir IR-spektroskopisch und durch eine röntgenographische Strukturanalyse charakterisiert haben. Raumgruppe P21/n, Z = 4, R = 4,3% für 5168 unabhängige beobachtete Reflexe. Die Gitterkonstanten betragen für ?65°C: A = 918,9; b = 2850,5; c = 1353,9 pm; β = 107,51°. Die Verbindung besteht aus PPh4+-Ionen und Anionen [MoNCl3[N(SiMe3)2]}–, in denen das Molybdänatom verzerrt tetragonal-pyramidal von dem Nitridoliganden in Apical-Position (r MoN = 165 pm), von drei Chloratomen und von dem N-Atom des Bis(trimethylsilyl)amido-Liganden (r MoN = 194 pm) umgeben ist. Das N-Atom des Amido-Liganden besitzt eine planare Umgebung. PPh4{MoNCl3[N(SiMe3)2]}, a Nitrido Amido Complex of Molybdenum (VI) PPh4{MoNCl3[N(SiMe3)2}] has been prepared by the reaction of PPh4[MoNCl4] with N,N,N′-Tris(trimethylsilyl)benzamidine in boiling dichloromethane, forming amber coloured crystals, which were characterized by their IR spectrum as well as by an X-ray structure determination. Space group P21/n, Z = 4, R = 0.043 for 5168 observed independent reflexions. The lattice dimensions are at ?65°C: A = 918.9; b = 2850.5; c = 1353.9 pm; β = 107.51°. The compound consists of PPh4+ ions and anions {MoNCl3[N(SiMe3)2]}– in which the complex molybdenum anion forms a distorted tetragonal pyramid with the nitrido ligand (r MoN 165 pm) in the apical position and the chlorine atoms along with the nitrogen atom of the amido ligand (r MoN 194 pm) in the basical positions. The N atom of the amido ligand has a planar geometry. 相似文献