首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
Vanadium(V) oxoazide [VO(N3)3] was prepared through a fluoride–azide exchange reaction between [VOF3] and Me3SiN3 in acetonitrile solution. When the highly impact‐ and friction‐sensitive compound [VO(N3)3] was reacted with 2,2′‐bipyridine, the adduct [(bipy)VO(N3)3] was isolated. The reaction of [VO(N3)3] with [PPh4]N3 resulted in the formation and isolation of the salt [PPh4]2[VO(N3)5]. The adduct [(bipy)VO(N3)3] and the salt [PPh4]23[VO(N3)5] were characterized by vibrational spectroscopy and single‐crystal X‐ray structure determination, making these compounds the first structurally characterized vanadium(V) azides.  相似文献   

2.
Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride–azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride–azide exchange resulted in the isolation of the adducts MO2(N3)2⋅2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2′‐bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4]2− were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X‐ray crystal structures.  相似文献   

3.
Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride–azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride–azide exchange resulted in the isolation of the adducts MO2(N3)2⋅2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2′‐bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4]2− were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X‐ray crystal structures.  相似文献   

4.
The binary zirconium and hafnium polyazides [PPh4]2[M(N3)6] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF4 by fluoride–azide exchange reactions with Me3SiN3 in the presence of two equivalents of [PPh4][N3]. The novel polyazido compounds were characterized by their vibrational spectra and their X‐ray crystal structures. Both anion structures provide experimental evidence for near‐linear M‐N‐N coordination of metal azides. The species [M(N3)4], [M(N3)5]? and [M(N3)6]2? (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels.  相似文献   

5.
Fluoride‐azide exchange reactions of Me3SiN3 with MnF2 and MnF3 in acetonitrile resulted in the isolation of Mn(N3)2 and Mn(N3)3?CH3CN, respectively. While Mn(N3)2 forms [PPh4]2[Mn(N3)4] and (bipy)2Mn(N3)2 upon reaction with PPh4N3 and 2,2′‐bipyridine (bipy), respectively, the manganese(III) azide undergoes disproportionation and forms mixtures of [PPh4]2[Mn(N3)4] and [PPh4]2[Mn(N3)6], as well as (bipy)2Mn(N3)2 and (bipy)Mn(N3)4. Neat and highly sensitive Cs2[Mn(N3)6] was obtained through the reaction of Cs2MnF6 with Me3SiN3 in CH3CN.  相似文献   

6.
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   

7.
The abstraction of the halogenide ligands in [Re(CH3CN)2Cl4]? should result in a solvent‐only stabilized ReIII complex. The reactions of salts of [Re(CH3CN)2Cl4]? with silver(I) and thallium(I) salts were investigated and the solid‐state structures of cis‐[Re(CH3CN)2Cl4]·CH3CN and cis‐[Re(NHC(OCH3)CH3)2Cl4] are described.  相似文献   

8.
Characterization of Distortional Isomers of the Anions Pentacyano-oxo-molybdate(IV) and of Tetracyano-aqua-oxo-molybdate(IV) in the Solid State. Crystal Structures of [(C6H5)4P]3[MoO(CN)5] · 7 H2O (green), [(C6H5)4As]2[MoO(OH2)(CN)4] · 4 H2O (blue), and [(C6H5)4P]2[MoO(OH2) (CN)4] · 4 H2O (green) Preparation of a series of salts containing the new pentacyano-oxo-molybdate(IV) anion is described: Cs2H[MoO(CN)5] (blue), [(CH3)4N]2H[MoO(CN)5] · 2 H2O (blue) and [Cr(en)3] [MoO(CN)5] · 4 H2O (green). The green [(C6H5)4P]3[MoO(CN)5] · 7 H2O crystallizes triclinic in the space group P1 . The molybdenum(IV) center is in an pseudo-octahedral environment of a terminal oxo-group (d(Mo?O); 1.705(4) Å), a CN? group in the trans-position (d(Mo? C): 2.373(6) Å), and four equatorial CN? groups (averaged d(Mo? C): 2.178 (Å). The blue and green salts exhibit v(Mo?O) stretching frequencies at 948 cm?1 and 920 cm?1, respectively. Blue and green salts containing the [MoO(OH2)(CN)4]2? anion and [(C6H5)4P]+ or [(C6H5)4As]+ cations have been prepared and characterized by single crystal crystallography. [(C6H5)4P]2[MoO(OH2)(CN)4] · 4 H2O (green) and [(C6H5)4As]2[MoO(OH2)(CN)4] · 4 H2O (blue) crystallize monoclinic in the space group C—P21/n. They are considered to be distortional isomers of the complex anion: the green species has a Mo?O bond distance of 1.72(2) Å whereas for the blue species d(Mo?O) = 1.60(2) Å is found; the corresponding v(Mo?O) frequencies are at 920 cm?1 and 980 cm?1.  相似文献   

9.
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   

10.
[PPh4][EI4] (E=As, Sb, Bi) salts were reacted with four and five equivalents of AgN3 to form tetraazidopnictates and pentaazidopnictates of the type [PPh4][E(N3)4] and [PPh4]2[E(N3)5], respectively. The synthesis of [PPh4][P(N3)4] was also attempted from the reaction of P(N3)3 with [PPh4]N3, but it yielded only the starting materials. Herein, we report the synthesis and structure elucidation of [PPh4][E(N3)]4 (E=As, Sb) and pentaazidobismuthate, stabilized as the dimethyl sulfoxide (DMSO) anion adduct, [PPh4]2[Bi(N3)5(dmso)]. Successive anion formation along the series E(N3)3+nN3? (n=1–3) and E(N3)5+N3? was studied by density functional theory.  相似文献   

11.
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   

12.
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   

13.
Synthesis and Crystal Structure of the Tetrameric Nitrido Complex [Cu(CH3CN)4]2[W4N4Cl14(CH3CN)2] . The title compound has been prepared by the reaction of CuCl with WNCl3 in acetonitrile solution, forming red, moisture sensitive crystals. They were characterized by IR spectroscopy and by an X-ray structure determination. Space group I2/a, Z = 4, 2 027 observed unique reflections, R = 0.049. Lattice dimensions at -80°C: a = 2 527.0, b = 971.9, c = 2 137.5 pm, β = 106.01°. The compound consists of [Cu(CH3CN)4]+ ions, which are arranged to form strands, and of anions [W4N4Cl14(CH3CN)2]2?, in which the tungsten atoms were located at the vertices of a square and are linked with one another via linear W?N? W bridges. Two of the four tungsten atoms have four chlorine atoms as terminal ligands, the other two tungsten atoms have three chlorine atoms and an acetonitrile molecule as terminal ligands.  相似文献   

14.
Bromo Complexes of Molybdenum(IV) [MoBr6]2? and [Mo2Br10]2?. Crystal Structure of (PPh3Me)2[MoBr6] · 2 CH2Br2 The bromomolybdates(IV) (PPh3Me)2[MoBr6] · 2 CH2Br2 and (PPh4)2[Mo2Br10] are obtained by reactions of molybdenum tetrabromide with PPh3MeBr and PPh4Br, respectively. They form black-brown, hydrolysis sensitive crystal powders. The crystal structure of (PPh3Me)2[MoBr6] · 2 CH2Br2 was determined by X-ray diffraction (2376 independent observed reflexions, R = 0.082). Crystal data: a = 1024, b = 1131, c = 1179 pm, α = 108.2°, β = 106.8°, γ = 99.0°, space group P1 , Z = 1. The compound consists of PPh3Me+ ions, CH2Br2 molecules and nearly octahedral [MoBr6]2? ions with MoBr bond lengths between 252.7 and 254.0 pm.  相似文献   

15.
The Crystal Structures of (NH4)2[ReCl6], [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN and [ReCl4(18)(Crown-6)] Brown single crystals of (NH4)2[ReCl6] are formed by the reaction of NH4Cl with ReCl5 in a suspension of diethylether. [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN crystallizes as brown crystal plates from a solution of ReCl5 in acetonitrile. Lustrous green single crystals of [ReCl4(18-crown-6)] are obtained by the reaction of 18-crown-6 with ReCl5 in a dichloromethane suspension. All rhenium compounds are characterized by IR spectroscopy and by crystal structure determinations. (NH4)2[ReCl6]: Space group Fm3 m, Z = 4, 75 observed unique reflections, R = 0.01. Lattice constant at ?70°C: a = 989.0(1) pm. The compound crystallizes in the (NH4)2[PtCl6] type, the Re? Cl distance is 235.5(1) pm. [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN: Space group P1, Z = 1, 2459 observed unique reflections, R = 0.12. Lattice dimensions at ?60°C: a = 859.0(1), b = 974.2(7), c = 1287.3(7) pm, α = 102.69(5)°, b? = 105.24(7)°, γ = 102.25(8)°. The structure consists of two symmetry-independent [ReCl2(CH3CN)4]+ ions with trans chlorine atoms, [ReCl6]2? ions, and included acetonitrile molecules. In the cations the Re? Cl bond lengths are 233 pm in average, in the anion they are 235 pm in average. [ReCl4(18-crown-6)]: Space group P21/n, Z = 4, 3 633 observed unique reflections, R = 0.06. Lattice dimensions at ?70°C: a = 1040.2(4), b = 1794.7(5), c = 1090.0(5) pm, b? = 108.91(4)°. The compound forms a molecular structure, in which the rhenium atom is octahedrally coordinated by the four chlorine atoms and by two oxygen atoms of the crown ether molecule.  相似文献   

16.
Crystal Structures of the Hexachlorometalates NH4[SbCl6], NH4[WCl6], [K(18‐crown‐6)(CH2Cl2)]2[WCl6]·6CH2Cl2 and (PPh4)2[WCl6]·4CH3CN The crystal structures of the title compounds were determined by single crystal X‐ray methods. NH4[SbCl6] and NH4[WCl6] crystallize isotypically in the space group C2/c with four formula units per unit cell. The NH4+ ions occupy a twofold crystallographic axis, whereas the metal atoms of the [MCl6]— ions occupy a centre of inversion. There exist weak interionic hydrogen bridges. [K(18‐crown‐6)(CH2Cl2)]2[WCl6]·6CH2Cl2 crystallizes in the orthorhombic space group R3¯/m with Z = 3. The compound forms centrosymmetric ion triples, in which the potassium ions are coordinated with a WCl3 face each. In trans‐position to it the chlorine atom of a CH2Cl2 molecule is coordinated so that, together with the oxygen atoms of the crown ether, coordination number 10 is achieved. (PPh4)2[WCl6]·4CH3CN crystallizes in the monoclinic space group P21/c with Z = 4. This compound, too, forms centrosymmetric ion triples, in which in addition the acetonitrile molecules are connected with the [WCl6]2— ion via weak C—H···Cl contacts.  相似文献   

17.
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   

18.
[Mo2(O2C–CH3)4 · 1/2 {(CH2)6N4} · 1/2 CH2Cl2] – a Donor‐Acceptor Complex with Supramolecular Structure Yellow single crystals of [Mo2(O2C–CH3)4 · 1/2 {(CH2)6N4} · 1/2 CH2Cl2] ( 1 ) have been obtained by the reaction of the silylated phosphaneimine Me3SiNPEt3 with [Mo2(O2C–CH3)4] in dichloromethane solution. 1 forms a three‐dimensional network with linear N–Mo:Mo–N and tetrahedral (CH2)6N4Mo4 moieties, which is topologically related with the PtS type. Space group P42/nnm, Z = 4, lattice dimensions at –70 °C: a = b = 1121.7(1), c = 1395.0(3) pm, R1 = 0.0413.  相似文献   

19.
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   

20.
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   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号