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1.
The Adduct of BiCl3 and Mo6Cl12: [BiCl] Dumbbells in the Structure of [BiCl][Mo6Cl14] MoCl3 reacts under decomposition to MoCl2 and Cl2 with BiCl3 in a sealed evacuated glass ampoule at 550 °C to form light red crystals of [BiCl][Mo6Cl14]. The crystal structure determination (monoclinic, C 2/c, a = 1268.1(4) pm, b = 1304.6(3) pm, c = 2571.9(8) pm, β = 91.79(3)°, Z = 8) shows that the structure is built of [(Mo6Cl8)Cl6] units containing nearly regular octahedral Mo6 clusters. These units are arranged in the motiv of a cubic closest packing. The octahedral interstices contain [BiCl] dumbbells with a Bi–Cl bond length of 249 pm. The coordination sphere of the Bi atom is completed by six weaker Bi–Cl-contacts of 275 to 308 pm length to a distorted monocapped trigonal prism. Neglecting the secondary Bi–Cl bonds, the title compound can be formulated as [(BiCl)2+][(Mo6Cl14)2–]. 相似文献
2.
Dithiolylium Chlorooxomolybdates(V): Synthesis and Crystal Structure of (C3Cl3S2)[MoOCl4] and (C3Cl3S2)[Mo2O2Cl7] The reaction of 3, 4, 5‐Trichlor‐1, 2‐dithiolylium chloride with MoOCl3 in dichlormethane under solvothermal conditions at 65 °C simultaneously yields the green tetrachlorooxomolybdate(V) (C3Cl3S2)[MoOCl4] and the yellow‐brown heptachlorodioxodimolybdate(V) (C3Cl3S2)[Mo2O2Cl7]. The crystal structures of both compounds contain nearly planar (C3Cl3S2)+ ions with a S—S bond length of 203 pm. The discrete [MoOCl4]— ion in the structure of (C3Cl3S2)[MoOCl4] has the shape of a square pyramid with the oxygen atom at the apex. The molybdenum atom is displaced by 58 pm from the basal plane towards the oxygen atom. The [Mo2O2Cl7]— ion in the structure of (C3Cl3S2)[Mo2O2Cl7] has the form of a face‐sharing double octahedron. It is formally composed of a [MoOCl4]— ion and a MoOCl3 molecule connected by one symmetrical and two unsymmetrical chloro bridges. The molybdenum atoms placed in the centers of such connected octahedra are 357 pm apart, indicating no Mo—Mo bond. 相似文献
3.
Preparation and Crystal Structure of β-[SeCl3][MoOCl4] The reaction of Se4[MoOCl4] and Te4[MoOCl4] with SOCl2 as solvent at 150 °C and 80 °C yields [SeCl3][MoOCl4] and [TeCl3][MoOCl4] respectively within 3 to 6 days as yellow-brown, moisture-sensitive crystals. [TeCl3][MoOCl4] was obtained in the already known monoclinic form, while β-[SeCl3][MoOCl4] crystallizes in a new polymorphic triclinic form (P1¯, Z = 2, a = 752.7(2), b = 812.8(2), c = 956.9(3) pm, α = 92.55(3)°, β = 111.63(2)°, γ = 107.39(3)°). The structure contains centrosymmetric tetranuclear units ([SeCl3]2[Mo2O2Cl8]) which are analogous to the entities found in the structure of [SCl3][MoOCl4]. The packing of the molecules in β-[SeCl3][MoOCl4] and [SCl3][MoOCl4] is distinctely different. 相似文献
4.
Ulrich Müller Elke Conradi Ute Patt-Siebel Meinolf Kersting Inge Schmidt Abderraouf Khabou Kurt Dehnicke 《无机化学与普通化学杂志》1988,560(1):93-104
Spectroscopic and Crystallographic Characterization of [Cl3PNPCl3][MoOCl4] and Crystal Structure of [Cl3PNPCl3][MoCl6] [Cl3PNPCl3][MoCl6] was obtained by reaction of MoCl5 with [Cl3PNPCl3]Cl or [Cl3PNPCl3][PCl6]. Its crystal was determined by X-ray diffraction (R = 0.072 for 889 observed reflexions). Lattice parameters: a = 811.9, b = 2086, c = 1016 pm, β = 101.7°, space group P21/c, Z = 4. The [Cl3PNPCl3]+ ions have a similar structure as in Cl3PNPCl3 [PCl6] with PNP angles of 139°, but the crystal structures of the two compounds are not isotypic. Partial hydrolysis of [Cl3PNPCl3][MoCl6] yields [Cl3PNPCl3][MoOCl4] which forms green, very moisture sensitive crystals. X-ray diffraction patterns of [Cl3PNPCl3][MoOCl4] single crystals exhibit planes of diffuse scattered radiation perpendicular to c*, which show the presence of a two-dimensional disorder. Additional sharp reflexions correspond to an averaged structure with the lattice parameters a = 1598.4, b = 1141.2 and c = 415.1 pm, Z = 2, space group Pba2. Refinement of the averaged 相似文献
5.
Wolfgang Einholz Knut Vaas Christoph Wieloch Bernd Speiser Tina Wizemann Markus Strbele Hans‐Jürgen Meyer 《无机化学与普通化学杂志》2002,628(1):258-268
Chemical and Cyclovoltammetric Investigation of the Redoxreactions of the Decahalodecaborates closo ‐[B10X10]2– and hypercloso ‐[B10X10]· – (X = Cl, Br)1). Crystal Structure Analysis of Cs2[B10Br10] · 2 H2O The oxidation of the decachloro‐closo‐decaborates(2–) Cs2[B10Cl10] or [Me4N]2[B10Cl10] with Tl(CF3COO)3 leads to the corresponding radical monoanion hypercloso‐[B10Cl10] · –, which was characterized by ESR and UV/Vis spectroscopy. [B10Cl10] · – does not dimerize like [B10H10] · – but it is reduced by acetonitrile to the dianion [B10Cl10]2–. Cs2[B10Cl10] reacts with stronger oxidation agents like CoF3 (in dichloromethane) or XeF2 (in perfluorhexane), respectively, to yield B9Cl9 and, in traces, B8Cl8. In opposite to this, the decabromoderivative Cs2[B10Br10] does not show any reaction with Tl(CF3COO)3 in acetonitrile or with CoF3 in CH2Cl2. The oxidation of the dianions [B10X10]2– (X = Cl, Br) was studied by electroanalytical methods (cyclic voltammetry, chronoamperometry, chronocoulometry). Formal potentials were determined for the two steps of the reaction, which do not seem to be affected by structural rearrangements. The crystal structure of Cs2[B10Br10] · 2 H2O was analyzed by single‐crystal X‐ray diffraction. Cs2[B10Br10] · 2 H2O crystallizes monoclinic (space group I2/a, (no. 15), Z = 8, a = 1361.54(9) pm, b = 1215.89(5) pm, c = 3108.4(2) pm, α = 90°, β = 97.916(8)°, γ = 90°). The closo‐cluster B10Br102– has a bicapped square antiprismatic structure with idealized D4d symmetry. 相似文献
6.
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
7.
The reaction of Se4[Mo2O2Cl8] with Se4[MCl6] (M = Zr, Hf) or of Se, SeCl4, MoOCl4, and MCl4 (M = Zr, Hf) at 120 °C in sealed evacuated glass ampoules gives (Se4)2[Mo2O2Cl8][MCl6] (M = Zr, Hf) in the form of dark‐green, air sensitive crystals in quantitative yield. The crystal structure analyses of both isotypic compounds (monoclinic, P21/c, Z = 2, a = 1336(2), b = 716(1), c = 1518(4) pm, β = 106.0(2)° for M = Zr; a = 1334.1(8), b = 715.03(9), c = 1518.2(3) pm, β = 106.00(2)° for M = Hf) show the presence of square‐planar Se42+, of dinuclear [Mo2O2Cl8]2—, and of almost regular octahedral [MCl6]2— ions. X‐ray crystallographic investigations on (Se4)2[Mo2O2Cl8][ZrCl6] give no hint for solid state phase transitions between —160 and 200 °C. This is in contrast to the related compounds Se4[Mo2O2Cl8] and Se4[ZrCl6] which both undergo phase transitions accompanied by reorientation of the cations and anions. (Se4)2[Mo2O2Cl8][ZrCl6] is paramagnetic and obeys the Curie‐Weiss law with a Weiss constant of —4(7) K indicating only weak interaction between the paramagnetic centres. The magnetic moment of 1.7(1) μB is consistent with the presence of MoV (d1 configuration) and supports the ionic formula. 相似文献
8.
The Layer Structure of Tl[CuAsO4] and Tl[CuPO4] with Layers of Thallium(I) with Stereoactive Lone Pair Single crystals of Tl[CuAsO4] and Tl[CuPO4] were prepared by reaction of oxygen with Tl/Cu/As and Tl/Cu/P alloys, respectively. The new isotypic compounds crystallize in spacegroup C2/c with Z = 8 and lattice constants a = 684.70(7) pm, b = 712.64(5) pm, c = 1822.4(2) pm, β = 92.76(1)° for Tl[CuAsO4] and a = 671.57(8) pm, b = 697.09(6) pm, c = 1789.1(2) pm, β = 93.12(1)° for Tl[CuPO4]. Square planar [CuO4]-units are connected by common corners to form undulated [CuO3]2-chains running along [010]. Interconnection of the chains by arsenate or phosphate groups results in the formation of anionic cuprate-arsenate- and cuprate-phosphate-slabs, respectively. Along [001] these slabs are alternating with double layers of thallium(I) ions in which the stereochemical activity of the Tl+ lone pair is apparent from an hemispheric coordination of thallium by oxygen. The structure is related to that of the orthorhombic form of KCuPO4. 相似文献
9.
Synthesis and Crystal Structure of Mo2<>NCl8 and Mo3N2Cl11 The reaction of MoCl5 with Cl3VNCl at 140 °C in a sealed glass ampoule yields air sensitive black crystals of the mixed valent molybdenum(V, VI) nitride chloride, Mo2NCl8. It crystallizes in the monoclinic space group P2/c with a = 996.1(1), b = 629.4(1), c = 1780.8(3) pm, β = 101.82(2)°, and Z = 4. The crystal structure consists of dinuclear C2‐symmetrical units [Cl2(N≡)Mo(μ2‐Cl)3Mo(≡N)Cl2]— and [Cl4Mo(μ2‐Cl)MoCl4]+, connected in an alternating sequence by asymmetric nitrido bridges Mo≡N‐Mo to form chains. The reaction of Cl3VNCl with MoCl3 at 140 °C affords Mo3N2Cl11, but for the prolonged reaction period, MoNCl3 is observed in addition. Mo3N2Cl11 can also be obtained from MoNCl3 and MoCl5 (2:1) at 140 °C. It forms orthorhombic, black crystals with the space group Pca21 and a = 1256.1(1), b = 1001.9(1), c = 1330.10(5) pm, and Z = 4. The structure contains the same dinuclear units [Cl2(N≡)Mo(μ2‐Cl)3Mo(≡N)Cl2]— as in Mo2NCl8, which in this case are connected with MoCl4+ moieties by asymmetric nitrido bridges Mo≡N‐Mo forming chains. In Mo2NCl8 the Mo‐N distances in the nearly linear nitrido bridges are 167.6(2), and 214.8(2) pm, whereas in case of Mo3N2Cl11 two sets of Mo‐N distances of 166, 8(4) and 214, 0(4) pm as well as 166, 9(4) and 211, 9(4) pm are observed. 相似文献
10.
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
11.
Petra Klinzing Aida El-Kholi Ulrich Müller K. Dehnicke Kurt Findeisen 《无机化学与普通化学杂志》1989,569(1):83-90
Reactions of N-Chloroacetoneimine with Molybdenum Pentachloride and Tungsten Hexachloride. Crystal Structure of Me2C?NH2[MoOCl4] WCl6 reacts with N-chloroacetoneimine under elimination of chlorine and formation of pentachloro-isopropylideneimino-tungsten(VI), Cl5W?N?CMe2, a brown-black crystal powder, which was characterized by i.r. spectroscopy. MoCl5 reacts in a similar way, although only a product mixture can be obtained. Partial hydrolysis of this mixture yields isopropylideneiminium-tetrachlorooxomolybdate(V), Me2C?NH2+[MoOCl4]?, of which the crystal structure was determined (2323 unique observed reflexions, R = 0.049). Space group P21/c, Z = 4, a = 878.6, b = 907.2, c = 1252.2 pm, β = 91.29°. The compound consists of Me2C?NH2+ ions with a planar arrangement of the skeletal atoms and a CN bond length of 126.7 pm and of dimeric, centrosymmetric anions [MoOCl4]22? having Mo atoms linked via asymmetric chloro bridges (MoCl distances 238.4 and 307.6 pm). The longer Mo? Cl contacts are located in the trans-positions of the terminal oxoligands (MoO distance 164 pm). 相似文献
12.
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
13.
MoCl4, ReCl4, and ReCl5 react with PCl5 in sealed glass ampoules at temperatures between 220° and 320° to [PCl4]2[Mo2Cl10] ( 1 ) [PCl4]2[Re2Cl10] ( 2 ), and [PCl4]3[ReCl6]2 ( 3 ). 2 crystallizes isotypically to the previously reported 1 and the respective titanium and tin containing analogues. The structure (triclinic, P1, Z = 1, a = 897.3(2), b = 946.0(2), c = 687.13(9) pm, α = 95.59(2)°, β = 95.80(2)°, γ = 101.07(2)°, V = 565.4(2) 106 pm3) is built of tetrahedral [PCl4]+ and edge sharing double octahedral [Re2Cl10]2– ions and can be derived from a hexagonal closest packing of Cl– ions with tetrahedral and octahedral holes partially filled by P(V) and Re(IV), respectively. 3 crystallizes isotypically to [PCl4]3[PCl6][MCl6] (M = Ti, Sn) (tetragonal, P 42/mbc, Z = 4, a = 1496.2(1), c = 1363.2(2) pm). Because no evidence was found for the presence of [PCl6]– ions, Re in 3 has to be of mixed valency with ReIV and ReV sharing the same crystallographic site. The structure can be derived from a cubic closest packing or alternatively from an only sparsely distorted body centered cubic arrangement of Cl– ions which is rarely found for anion arrays. The tetrahedral and octahedral holes are partially filled by PV and MIV/V, respectively. Magnetic measurements show all three compounds to be paramagnetic and confirm the oxidation state IV for Mo and Re in 1 and 2 and the mixed valence (IV/V) for Re in 3 . 相似文献
14.
Zincselenide- and Zinctellurideclusters with Phenylselenolate- and Phenyltellurolateligands. The Crystal Structures of [NEt4]2[Zn4Cl4(SePh)6], [NEt4]2[Zn8Cl4Se(SePh)12], [Zn8Se(SePh)14(PnPr3)2], [HPnPr2R]2[Zn8Cl4Te(TePh)12] (R = nPr, Ph), and [Zn10Te4(TePh)12(PR3)2] (R = nPr, Ph) In the prescence of NEt4Cl ZnCl2 reacts with PhSeSiMe3 or a mixture of PhSeSiMe3/Se(SiMe3)2 to form the ionic complexes [NEt4]2[Zn4Cl4(SePh)6] 1 or [NEt4]2[Zn8Cl4Se(SePh)12] 2 respectively. The use of PnPr3 instead of the quarternary ammonia salt leads in toluene to the formation of crystalline [Zn8Se(SePh)14(PnPr3)2] 3 . Reactions of ZnCl2 with PhTeSiMe3 and tertiary phosphines result in acetone in crystallisation of the ionic clusters [HPnPr2R]2[Zn8Cl4Te(TePh)12] (R = nPr 4 , Ph 5 ) and in THF of the uncharged [Zn10Te4(TePh)12(PR3)2] (R = nPr 6 , Ph 7 ). The structures of 1–7 were obtained by X-ray single crystal structure. ( 1 : space group P21/n (No. 14), Z = 4, a = 1212,4(2) pm, b = 3726,1(8) pm, c = 1379,4(3) pm β = 99,83(3)°; 2 space group P21/c (Nr. 14), Z = 4, a = 3848,6(8) pm, b = 1784,9(4) pm, c = 3432,0(7) pm, β = 97,78(3)°; 3 : space group Pnn2 (No. 34), Z = 2, a = 2027,8(4) pm, b = 2162,3(4) pm, c = 1668,5(3) pm; 4 : space group P21/c (No. 14), Z = 4, a = 1899,8(4) pm, b = 2227,0(5) pm, c = 2939,0(6) pm, β = 101,35(3)°; 5 : space group space group P21/n (No. 14), Z = 4, a = 2231,0(5) pm, b = 1919,9(4) pm, c = 3139,5(6) pm, β = 109,97(4)°; 6 : space group I41/a (No. 88), Z = 4, a = b = 2566,0(4) pm, c = 2130,1(4) pm; 7 : space group P1¯ (No. 2), Z = 2, a = 2068,4(4) pm, b = 2187,8(4) pm, c = 2351,5(5) pm, α = 70,36°, β = 84,62°, γ( = 63,63°) 相似文献
15.
Synthesis and Crystal Structure of (PPh4)2[Mo2NCl9]2, a μ-Nitrido Complex with Molybdenum (V) and (VI) The title compound is formed as a by-product in the partial oxidation of Mo2NCl7 with chlorine in POCl3 solution, when the reaction mixture is treated with PPh4Cl. The crystals, which are sensitive to moisture, are black in reflectance and red in transmittance. A more effective synthesis is the direct reaction of PPh4[MoNCl4] with MoCl5 in dichloro methane. (PPh4)2[Mo2NCl9]2 was characterized by the i.r. spectrum and by a structural analysis with X-ray data. The compound crystallizes triclinic in the space group P1 with two formula units per unit cell (9225 independent observed reflexions, R = 0.058). The cell parameters are (20°C): a = 1144 pm, b = 1517 pm, c = 2000 pm, α = 79.8°, β = 80.1°, γ = 72.1°. (PPh4)2[Mo2NCl9]2 consists of PPh4⊕ cations and the anions [Mo2NCl9]222?, which dimerize via chloro bridges with Mo? Cl bons lengths of 243 pm and 287 pm. In the [Mo2NCl9]22? units the molybdenum atoms are linked by MoVI?N? MoV bridges (bond angles 179° and 174°, resp.) with Mo? N bond lengths of 167 pm and 212 pm. 相似文献
16.
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
17.
Thiochloro Anions of Molybdenum (IV). Crystal Structure of (NEt4)3[Mo3(μ3-S)(μ-S2)3Cl6]Cl μ CH2Cl2. Crystal Structure, Magnetic Properties, and EPR-Spectrum of (NEt4)2 [Mo2(μ-S2)(μ-Cl)2Cl6] From molybdenum pentachloride and tetraethylammonium hydrogensulfide in CH2Cl2 an insoluble product of composition (NEt4)2[Mo2S3Cl9] was obtained along with a brown solution, from which (NEt4)2[Mo2(S2)Cl8] was crystallized. The insoluble product and NEt4Cl react in CH2Cl2 to yield, among others, (NEt4)3[Mo3(S)(S2)3Cl6]Cl · CH2Cl2. The latter crystallizes in the orthorhombic space group Pnma, a = 2495.8, b = 1501.2, c = 1295.6 pm, Z = 4. According to the crystal structure determination (3070 observed reflexions, R = 0.049) the [Mo3(S)(S2)3Cl6]2? ion consists of an Mo3 triangle with Mo? Mo bonds, each side of the triangle is bridged by disulfido groups and one sulfur atom is capped over the Mo3 triangle; the single chloride ion is looseley associated to three S atoms. (NEt4)2[Mo2(S2)Cl8] also crystallizes in the space group Pnma, a = 1425.6, b = 1129.9, c = 2004.7 pm, Z = 4; structure determination with 1703 observed reflexions, R = 0.061. In the [Mo2(S2)Cl8]2? ion the Mo atoms are bridged via one disulfido group and two chlorine atoms. There is a Mo? Mo bond, but according to the magnetic properties and the EPR spectrum each Mo atom still possesses one unpaired electron. 相似文献
18.
Synthesis and Structure of Mo2NCl7 The reaction of VN with MoCl5 at 175 °C in a sealed glass ampoule yields the molybdenum(V) nitride chloride Mo2NCl7 in form of air sensitive black crystals with the triclinic space group P1¯ and a = 905.7(8); b = 975.4((6); c = 1283.4(8) pm, α = 103.13(4)°; β = 109.83(5)° und γ = 98.58(5)°. The crystal structure is built up from dinuclear units [Mo2N2Cl7]3— and [Mo2Cl7]3+, which are connected by asymmetric nitrido bridges to form endless chains. Within both dinuclear units the Mo atoms are bridged by three Cl atoms resulting in a Mo‐Mo distance of 349.2(3) pm in the unit [Mo2N2Cl7]3—. In case of [Mo2Cl7]3+, however, a shorter Mo‐Mo distance of 289.4(3) pm is observed, which can be interpreted by a single bond. Correspondingly a reduced magnetic moment of 0.95 B.M. per Mo atom is observed. 相似文献
19.
Reaction of [Mo6Cl8]X4 with N-Bases [Mo6Cl8]X4 (X = Cl, Br, I) in ethanol solution by titration with Ag+ showed 4 labil X atoms. The displacement of X? especially by F? accelerates the titration decisively. Conductivity measurements in ethanol or acetone showed that [Mo6Cl8]X4 at 25°C behave as weak 1:1-electrolytes. Solutions of [Mo6Cl8]X4 in DMF heated up to 60°C and than lowered to 25°C showed that the compounds in this solvent behave as (potential) strong 2:1-valent electrolytes. From the following compounds the labil halides have been determined by titration with Ag+: [Mo6Cl8]X4(Py)2 (X = Cl, Br), [Mo6Cl8]X4(bipy)2 (X = Cl, Br, I), [Mo6Cl8]X4(Phenpy)2 (X = Cl, Br, I), (PyH)2[Mo6Cl8]X6 (X = Cl, Br); (bipyH)2[Mo6Cl8]I4Cl2. Always 4 (respectively 6) labil halides have been observed; exception [Mo6Cl8]Cl4(Py)2 in acetone (2 labil Cl). Lattice constants and mole volumina for the adducts with pyridin and bipyridin have been determined. The adducts with bipyridin and phenylpyridin are isotypic. Conductivity measurements have been made in different solutions. The decomposition on the thermobalance showed that in [Mo6Cl8]Cl4(Py)2 the bond of pyridin is weak. The 2 pyridin molecules are evolved at the same time. However [Mo6Cl8]I4(Bipy)2 loses 1 bipyridin only. (PyH)2[Mo6Cl8]X6 formed during the first decomposition step the novel compounds (PyH) [Mo6Cl8]X5 (X = Cl, Br). Both compounds are isotypic. They behave in ethanol solution as strong 1:1-valent electrolytes. 相似文献
20.
Na2[Pr4O2]Cl9 and K2[Pr4O2]Cl9, the First Reduced Quaternary Praseodymium Chlorides with Anti-SiS2 Analogous [Pr4/2O] Chains The compounds A2[Pr4O2]Cl9 (A = Na, K) are the first reduced quaternary praseodymium chlorides with anti-SiS2 analogous [Pr4/2O] chains. Synthesis took place in the temperature range from 900 to 600°C in silica-jacketed niobium containers from Pr metal, PrCl3, PrOCl and NaCl (KCl) as starting materials. The X-ray structure analysis of a single crystal of Na2[Pr4O2]Cl9 (monoclinic, P21/m (No. 11), Z = 2, a = 812.2(2) pm, b = 1 134.1(2) pm, c = 937.6(2) pm, β = 106.51(2)°, R = 0.048, Rw = 0.037) exhibits trans-edge connected chains of [Pr4/2O] tetrahedra running along [001] which are connected by surrounding common chloride ions forming layers parallel to (001). These layers are connected by further chloride ions to a three-dimensional network. The sodium ions surrounded by a heavily distorted octahedron of chloride ions are placed between the layers. The X-ray structure analysis of a single crystal of the otherwise isotypic K2[Pr4O2]Cl9 (monoclinic, P21/m (No. 11), Z = 2, a = 820.6(2) pm, b = 1 133.2(4) pm, c = 949.2(3) pm, β = 103.94(2)°, R = 0.073, Rw = 0.054) shows that potassium is coordinated by nine chloride ions. 相似文献