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1.
Synthesis and Crystal Structure of (PPh4)2[Mo2(S2)2Cl8] · 2 CH3CN and its Topotactic Transformation to (PPh4)2[Mo2(S2)2Cl8] MoS2Cl3 was prepared from molybdenum and S2Cl2 at 200 °C. Its reaction with PPh4Cl in acetonitrile yielded (PPh4)2[Mo2(S2)2Cl8] · 2 CH3CN. In vacuum or upon warming, it loses the acetronitrile without degradation of the crystals. According to the X-ray crystal structure determinations both compounds, with and without acetonitrile, are triclinic. They contain the same [Cl4Mo(μ-S2)2MoCl4]2– ions, in which the Mo atoms are joined by two disulfido groups and an Mo–Mo bond. Details of the crystal packings and their topotactic transformation are given.  相似文献   

2.
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   

3.
Synthesis and Structure of μ-Sulfido-μ-disulfido-octabromoditungstate(V), [W2S3Br8]?2 Tungsten hexabromide reacts with H2S in dichloromethane yielding a brown product which, by addition of tetraphenylphosphonium bromide in CH2Cl2, is converted to brown, crystalline (PPh4)2[Br4W(μ-S)(μ-S2)WBr4] · CH2Cl2 · CH2S. Its IR spectrum is reported, its crystal structure was determined by X-ray diffraction (2330 reflexions, R = 0.097). Crystal data: orthorhombic, Pnma, a = 1 766.5, b = 2 412.7, c = 1 416.3 pm, Z = 4. In the diamagnetic [W2S3Br8]2? ions the two W atoms are linked via a sulfido and a disulfido bridge and by a W? W bond.  相似文献   

4.
The title compound was prepared by the reaction of Mo_3S_4(dtp)_4(H_2O)[ctp=S_2P(OEt)_2]with NaOAc·3H_2O and C_4H_8NCS_2NH_4.Crystallographic data:[Mo_3(μ_3-S)(μ-S)_2(μ-OAc)-(S_2CNC_4H_8)_3(O)_2]·0.5CH_2CI_2·2H_2O,Mr=980.18,triclinic,space group P,α=12.360(3),b=16.653(6),c=9.206(2)A,α=101.97(2),β=108.32(2),γ=86.14(3)°.V=1759.6(9)A~3,Z=2,Dc=1.85 g/cm~3,F(000)=962,μ(Mo K_α)=16.53 cm~(-1).Final R=0.044 for 4301 reflections with I≥3σ(I).This compoundmay be regarded as a mixed-valent trinuclear molybdenum cluster{Mo_2(V)Mo(Ⅳ)(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2}.The Mo-Mo distances are 2.783(1),2.833(1)and 3.374(2)A in the Mo_3non-equilateral triangle and there exist only two Mo-Mo bonds.The cluster was obtained by oxi-dation and ligand substitution of{Mo_3(μ_3-S)(μ-S)_3[μ-S_2P(OEt_2)][S_2P(OEt)_2]_3(H_2O)}.  相似文献   

5.
Thiohalo Compounds of Niobium and Tantalum: NbSCl3, TaSCl3, [NbSCl5]2?, [TaSCl5]2?, [NbSBr4]?. Crystal Structures of (PPh4)2[NbSCl5] · 2 CH2Cl2 and NEt4[NbCl6] NbSCl3 can be obtained from NbCl5 by reaction with H2S or bistrimethylsilyl sulfide in a suspension of CCl4 or CH2Cl2, respectively; in the latter case the product contains a rest of trimethylsilyl groups. This also applies for TaSCl3, NbSBr3 and TaSBr3, which are formed from the metal pentahalides and S(SiMe3)2. NEt4[NbSCl4] is formed together with NEt4[NbCl6] in the reaction of NbCl5 with NEt4SH in CH2Cl2. PPh4[NbCl6] reacts with S(SiMe3)2 in dichloromethane yielding (PPh4)2[NbSCl5] · 2 CH2Cl2, whereas PPh4[NbSBr4] is obtained from PPh4[NbBr6] and S(SiMe3) under the same conditions. (PPh4)2[TaSCl5] · 2 CH2Cl2 was obtained from TaSCl3 and PPh4Cl in CH2Cl2. According to an X-ray crystal structure determination (PPh4)2[NbSCl5] · 2 CH2Cl2 crystallizes in the β-(AsPh4)2[UCl6] · 2 CH2Cl2 type with positionally disordered, octahedral anions. Crystal data: a = 1 021.7, b = 1120.4, c = 1 243.3 pm, α = 70.77, β = 80.24, γ = 80.54°, space group P1 , Z = 2; 2462 unique observed reflexions, R = 0.036. NEt4[NbCl6] crystallizes isotypic to NEt4[WCl6], a = 723.5, b = 1 018.0, c = 1 174.6 pm, β = 100.07°, space group P21/n, Z = 2; 1 875 reflexions, R = 0.075.  相似文献   

6.
Preparation of trans-[Mo6Cl8]Cl4Br22? Starting from Crystalline [Mo6Cl8]Cl4(H2O)2 and Crystal Structure of [(C6H5)4As]2[Mo6Cl8]Cl4Br2 The synthesis of the title compound is successful if the crystallized [(Mo6Cl8)Cl4(H2O)2] containing the H2O molecules in trans-position reacts with HBr + [(C6H5)4As]Br in ethanol in a heterogeneous reaction. The X-ray structure investigation confirms the existence of discrete trans-Br-substituted cluster anions of composition [(Mo6Cl8)Cl4Br2]2? in the crystal. The reaction in homogeneous solutions proceeds to Br-enriched compounds. [(C6H5)4As]2[(Mo6Cl8)Cl4Br2] crystallizes in the triclinic space group P¯1 with a = 11.071(2), b = 11.418(2), c = 12.813(2) Å, α = 116.10(2), β = 95.27(2) and γ = 94.41(2)° (?133°C). The crystal structure at ?133°C was determined from single crystal X-ray diffraction data (R1 = 0.026). The [(Mo6Cl8)Cl4Br2]2?-anions are not completely ordered but distributed statistically among the three positions which are possible within the limits of the ordered [Mo6Cl8]-cores (ratio 11:5:4). The frameworks of the anions consist of Mo6 cluster units with (slightly distorted) octahedral arrangement of the metal atoms (d(Mo? Mo): 2.600(1) up to 2.614(1) Å), which are coordinated by the halogeno ligands in a square-pyramidal manner. The details of the structure will be discussed and compared with similar [(Mo6X8)Y4] cluster units (X, Y ? Cl, Br).  相似文献   

7.
Nitrosyl Complexes of Molybdenum (+II). Crystal Structures of [Mo(NO)Cl3 · POCl3]2 and [AsPh4]2[Mo(NO)Cl5] · 2 CH2Cl2 Solutions of MoCl5 in POCl3 react with NOCl forming the nitrosyl compound Mo(NO)Cl3 · 2POCl3 ( I ), which in CH2Cl2 cleaves off one solvate molecule, yielding the dimeric complex [Mo(NO)Cl3 · POCl3]2 ( II ). Reaction with AsPh4Cl in dichloro methane leads to the nitrosyl complexes AsPh4[Mo(NO)Cl4] · CH2Cl2 ( III ) and [AsPh4]2[Mo(NO)Cl5] · 2CH2Cl2 ( IV ), respectively. The i.r. spectra are recorded and assigned. [Mo(NO)Cl3 · POCl3]2 crystallizes monoclinic in the space group P21/c with two dimeric units per unit cell. The crystal structure was determined by X-ray diffraction methods (R = 0.040; 1391 observed, independent reflexions). Complex II is linked by chlorine bridges, forming a dimeric, centrosymmetric molecule of symmetry Ci. The N? O bond of the nitrosyl ligand is extremely short (108 pm), the Mo? N bond (181 pm) corresponds to a double bond. In trans position to the NO ligand, which is coordinated in linear array, there is the O atom of the solvate molecule POCl3. [AsPh4]2[Mo(NO)Cl5] · 2 CH2Cl2 crystallizes triclinic in the space group P1 with two units per unit cell (R = 0.039; 1967 observed, independent reflexions). The molybdenum atom is coordinated octahedrally by five Cl ligands and a nitrosyl group, as well coordinated in linear array (Mo? N? O 174°). The nitrosyl ligand exerts a significant trans-effect (r Mo? Cl(trans) = 247 pm, r MoCl4(eq)(average) = 239 pm).  相似文献   

8.
Reaction of 2,2-Dimethylpropylidynephosphine with Molybdenum Pentachloride; Crystal Structure of [Mo2Cl6(α,α′-dipyridyl)3] 2,2-Dimethylpropylidynephosphine and molybdenum pentachloride dissolved in POCl3 react with oxydation of the phosphorus and reduction of the molybdenum atom to give the alkyne complex [Mo2Cl4(μ-Cl)2(μ-H9C4? C?C? C4H9)(OPCl3)2]. Addition of α,α′-dipyridyl or of methyltriphenylphosphonium chloride in dichloromethane results in a displacement of the ligands POCl3 and H9C4? C?C? C4H9 from this complex and in the formation of [Mo2Cl6(dipy)3] or [(H5C6? )3P? CH3]3[Mo2Cl9]. Besides the latter compound small amounts of [(H5C6? )3P? CH3]2[MoCl6] can be isolated from the reaction mixture. [Mo2Cl6(dipy)3] which has already been prepared by other methods crystallizes in the monoclinic space group P21/c with {a = 1612; b = 148; c = 1296 pm; γ 109.3°; Z = 4} at 20°C. As shown by a crystal structure determination the complex is built up from [MoCl2(dipy)2]+ cations and [MoCl4(dipy)]? anions. The molybdenum atoms are both octahedrally surrounded. With average values of 238 and 243 pm the Mo? Cl bond distances in the cation, where a cis-arrangement of the chlorine atoms is observed, and in the anion differ significantly from each other. [Mo2Cl6(dipy)3] which has already been prepared by other methods crystallizes in the monoclinic space group P21/c with {a = 1612; b = 148; c = 1296 pm; γ = 109.3°; Z = 4} at 20°C. As shown by a crystal structure determination the complex is built up from [MoCl2(dipy)2]+ cations and [MoCl4(dipy)]? anions. The molybdenum atoms are both octahedrally surrounded. With average values of 238 and 243 pm the Mo? Cl bond distances in the cation, where a cis-arrangement of the chlorine atoms is observed, and in the anion differ significantly from each other.  相似文献   

9.
(PPh3Me)2[{MoCl4(NO)}2(μ-S2 N2)]; Synthesis, I.R. Spectrum, and Crystal Structure The title compound is prepared by the reaction of (PPh3Me)2[MoCl3(NO)2]2 with trithiazyl chloride in CH2Cl2 solution. It forms yellow, only slightly moisture sensitive crystals, which are characterized by their IR spectrum as well as by an X-ray structure determination. (PPh3Me)2[{MoCl4(NO)}2 (μ-S2N2)] crystallizes triclinic in the space group P1 with one formula unit in the unit cell (5952 independent, observed reflexions, R = 0.045). The lattice dimensions are at 20°C: a = 1021, b = 1143, c = 1243, pm; α = 64,15°, β = 68.24°, γ = 80.85°. The compound consists of PPh3Me⊕ cations and anions [{MoCl4(NO)}2(μ-S2N2)]2?, in which the molybdenum atoms are bridged by the N-atoms of the planar S2N2 ring. In the trans-positions of these N-atoms the linear nitrosyl groups are coordinated via Mo ? N ? O .  相似文献   

10.
Synthesis and Crystal Structure of (PPh4)2[Mo2Cl10] The title compound is obtained in the reaction of [MoCl4(Ph? C?C? Ph)]2 with tetraphenylphosphonium chloride in dichloro methane, forming brown crystals. It is characterized by the i.r. spectrum and a crystal structure analysis by the aid of X-ray diffraction data. The complex crystallizes triclinic in the space group P1 with one formula unit per unit cell. The cell dimensions are a = 1122 pm, b = 1137 pm, c = 1283 pm; α = 63.4°, β = 69.1°, γ = 86.5°. The crystal structure determination (2959 observed, independent reflexions, R = 4.5%) shows the constants of the unit cell to consist of on centrosymmetric anion, two cations and one disordered molecule of dichloro methane. The distance Mo? Mo in the anion is 380 pm, which excludes direct magnetic interaction between the molybdenum atoms.  相似文献   

11.
Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH and (C18H36N2O6Na)2[Mo6Cl8(OC6H5)6] . The reaction of Na2[Mo6Cl8(OCH3)6] and 2,2,2-crypt yields (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6 CH3OH ( 1 ), which is converted to (C18H36N2O6Na)2[Mo6Cl8(OC6H5)6] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo6Cl8i(ORa)6]2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo6Cl8(OC6H5)6]2? is investigated by means of UV/VIS spectroscopy and EHMO calculations.  相似文献   

12.
Thiochlorowolframates with Tungsten(V) and (VI). Crystal Structures of PPh4[WSCl4] and (PPh4)2[WS2Cl4] · 2 CH2Cl2 Diamagnetic (NEt4)2[WSCl4]2, having tungsten atoms linked via sulfur atoms, is obtained by the reaction of WCl5 with NEt4SH as well as by the reduction of WSCl4 with NEt4I in dichloromethane. If the reduction is performed with PPh4I, PPh4[WSCl4] with monomer anions is formed. Reaction of WCl6 with H2S in dichloromethane yields brown, insoluble WS2Cl2 which has terminal W?S groups and bridging W? S? W groups according to its IR spectrum. WS2Cl2 and PPh4Cl react to afford PPh4[WS2Cl3] · 2 CH2Cl2 and (PPh4)2[WS2Cl4] · 2 CH2Cl2. IR spectra are reported. The crystal structures of PPh4[WSCl4] and (PPh4)2[WS2Cl4] · 2 CH2Cl2 were determined by X-ray diffraction. PPh4[WSCl4]: tetragonal, space group P4/n, Z = 2, a = 1292.3 pm, c = 763.2 pm; R = 0.054 for 898 observed reflexions. The [WSCl4]? ion has the structure of a square pyramid with a rather short W?S bond of 206 pm length. (PPh4)2[WS2Cl4] · 2 CH2Cl2: triclinic, space group P1 , a = 1017.7, b = 1114.5, c = 1243.4 pm, α = 70.61, β = 79.73, γ = 80.80°; R = 0.076 for 1804 reflexions. The [WS2Cl4]2? has cis configuration; as it is situated on an inversion center it shows positional disorder.  相似文献   

13.
Thiocomplexes of Molybdenum. Crystal Structure of a Mixed Single Crystal (PPh3Me)2[Mo2Br6(NO)4]/(PPh3Me)2[Mo2Br6S2(NO)2] The reactions of (PPh4)2MoS4 with MoBr4 and MoBr2(NO)2 resp. lead to the binuclear complexes (PPh4)2[S2MoS2MoBr3(SMe2)] and (PPh4)[S2MoS2MoBr2(NO)2], in which the molybdenum atoms are linked by sulfido bridges. The preparation of (PPh3Me)2S6 and (AsPh4)2S7 from Na2S4 and PPh3MeBr, and AsPh4Cl, respectively, in ethanol solution is described. Disulfido briges are a feature of (AsPh4)2[Mo2Br6(S2)2(SMe2)2], which is obtained from MoBr4(SMe2)2 and (AsPh4)2S7. Mixed single crystals containing 2/3 (PPh3Me)2[Mo2Br6(NO)4] and 1/3 (PPh3Me)2[Mo2Br6S2(NO)2] are formed in the reaction of MoBr2(NO)2 with (PPh3Me)2S6, as shown by X-ray single crystal structure determination. The compound crystallizes monoclinic in the space group C2/c (Internat. Tab. Nr. 15) with four formula units per unit cell (2351 independent observed reflexions, Rw = 0.037). The cell parameters are a = 1603 pm, b = 1549 pm, c = 1863 pm; β = 92.2°. The complexes consist of PPh3Me cations and the dimeric anions [Mo2Br6(NO)4]2? and [Mo2Br6S2(NO)2]2? which occur in the ratio 2:1. In these the molybdenum atoms are connected via MoBr2Mo bridges of slightly different lengths (Mo? Br 265 pm and 267 pm) forming a controsymmetric double octahedron. All molybdenum atoms have two terminal bromo ligands with Mo? Br bond lengths of 258 pm and 260 pm; in the [Mo2Br6(NO)4]2? ion each molybdenum has two covalently bonded nitrosyl groups on cis-position with Mo? N bond lengths of 183 pm. In the [Mo2Br6S2(NO)2]2? ion one of the two nitrosyl groups at each metal atom is substituted by a terminal sulfido ligand with a Mo? S bond length of 240 pm. The i.r. spectra are reported.  相似文献   

14.
Synthesis and Crystal Structures of (PPh4)2[In(S4)(S6)Cl] and (PPh4)2[In(S4)Cl3] InCl and PPh4Cl yield (PPh4)2[In2Cl6] in acetonitrile. This reacts with Na2S4 in presence of PPh4Cl, forming (PPh4)2[In(S4)(S6)Cl]. Its crystal structure was determined by X-ray diffraction (R = 0.075, 2 282 observed reflexions). It is isotypic with (PPh4)2[In(S4)(S6)Br] and contains anions with trigonal-bipyramidal coordination of In, Cl occupying an axial position, and the S4 and S6 groups being bonded in a chelate manner. The reaction of (PPh4)2[In2Cl6] and sulfur in acetonitrile yielded (PPh4)2[InCl5] and (PPh4)2[In(S4)Cl3]. The crystal structure analysis of the latter (R = 0.072, 4 080 reflexions) revealed an anion with distorted trigonal-bipyramidal coordination of In, the S4 group occupying one axial and one equatorial position; the S4 group shows positional disorder.  相似文献   

15.
(PPh4)[(ReO2S2)CuI] and (NEt4)2[ReOS3)Cu3Cl4]: Fixation of the up to now not Isolated Ions [ReO2S2]? and [ReOS3]? Utilizing the Stability of the CuS2(Re) and Cu3S3(Re) Fragments (PPh4)[(ReO2S2)CuI] ( 1 ) and (NEt4)2[ReOS3)Cu3Cl4] ( 2 ) containing the up to now not isolated oxothioperrhenate ions [ReO2S2]? and [ReOS3]? as ligands, have been prepared by the reaction of (NEt4)[ReS4] with PPh3 and CuI in acetone in the presence of (PPh4)I (( 1 )) or with CuCl in CH2Cl2 in the presence of (NEt4)Cl (( 2 )), respectively. 1 and 2 have been characterized by X-ray structure analysis, elemental analysis and spectroscopic studies (IR, UV/Vis). The electronic spectra show bands which can approximately be assigned to interesting low-energy charge-transfer-transitions of the type d(Cu) → d(Re). For crystal data see Inhaltsübersicht.  相似文献   

16.
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   

17.
Mo2O3Cl4(Pyridine)4 · CH2Cl2. Synthesis, IR Spectrum, and Crystal Structure Reduction of MoO2Cl2(pyridine)2 with triphenylphosphane in toluene and recrystallisation from CH2Cl2 yields brown crystal needles of the complex Mo2O3Cl4(pyridine)4 · CH2Cl2. The compound crystallizes monoclinic in the space group P21/c with four formula units per unit cell of the dimensions a = 1 234.6 pm; b = 1 593 pm, c = 1 522.3 pm and β = 105.66° A structural investigation by X-ray methods (3 276 independent observed reflexions, R = 0.033) reveals the molecule with two molybdenum atoms in a distorted octahedral coordination linked by an almost linear Mo? O? Mo bridge with bond distances of 167 and 168 pm, respectively. The chlorine atoms are located in trans-position to the oxygen atoms which have different trans effects: The Mo? Cl bond opposite the bridge (length 242 pm) is 8 pm shorter than the bond in trans position to the terminal oxo ligands. The pyridine nitrogen atoms are in trans position to each other and complete the coordination of the molybdenum atoms. The i.r. spectrum of the compound is reported.  相似文献   

18.
The Molecular Complex Tris(μ4‐disulfido)‐hexa‐μ2‐chloro‐hexapalladium [Pd6(S2)3Cl6] A new hexameric form of PdSCl have been obtained by reaction of Pd metal with sulfur in SCl2 solution at 180 °C in a closed silica ampoule. The monoclinic crystal structure of β‐PdSCl (space group P21 /m; a = 7.766(2)Å; b = 11.941(2)Å; c = 9.136(3)Å; β = 110.57(3)°; Z =12) is built up by clusters [Pd6(S2)3Cl6] with nearly D3h symmetry. In the molecular units six Pd atoms form a trigonal prism with three S2 disulfide groups in front of the side faces. The fourfold coordination of the Pd atoms is completed by 6 Cl atoms forming μ2 bridges.  相似文献   

19.
Chlorothionitrene Complexes of Rhenium. Crystal Structure of AsPh4[ReCl4(NSCl)2] · CH2Cl2 Rhenium pentachloride reacts in POCl3 solution with (NSCl)3 forming the chlorothionitrene complexes [(Cl3PO)ReCl4(NSCl)] ( I ) and [(Cl3PO)ReCl3(NSCl)2] ( II ). I reacts with AsPh4Cl in CH2Cl2 solution under abstraction of SCl2 and POCl3, yielding AsPh4[ReNCl4], while II forms the complex AsPh4[ReCl4(NSCl)2] · CH2Cl2. The i.r. spectra of the compounds are discussed and assigned. The crystal structure of AsPh4[ReCl4(NSCl)2] · CH2Cl2 was determined and refined with X-ray diffraction data (R = 0.031 for 2785 reflexions). It crystallizes in the space group Pī with two formula units per unit cell; the lattice constants are a = 1119, b = 1144, c = 1473 pm, α = 77.6, β = 70.8 and γ = 71.2°. The two NSCl ligands have cis arrangement with nearly linear Re?N?S groups, with interatomic distances corresponding to double bonds. The Re? Cl bonds are somewhat longer than usual and show no trans-effect; this is possibly due to Cl…?H? C bridges.  相似文献   

20.
NEt4[Re3Cl10(H2O)2] · 2 H2O ( 1 ) was obtained from hydrochloric acid solutions of ReCl3 and tetraethylammonium chloride, NEt4Cl, by isothermal evaporation as dark red crystals. 1 crystallizes in the orthorhombic crystal system, space group Pnma, Z = 4, with a = 1838,7(2), b = 1456.9(1), c = 972.08(7) pm, Vm = 391.81(6) cm3 · mol?l. The crystal structure consists of [Re3Cl10(H2O)2]? anions that are arranged in the fashion of a hexagonal closest-packing of spheres. These are held together by partially disordered NEt4+ cations and are bound into a hydrogen bonding system with the crystal water.  相似文献   

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