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1.
Syntheses and Crystal Structure Analyses of [SbI3(SbMe3)(THF)]2 and [Li(THF)4]2[Bi2Cl8(THF)2] The reaction of Me3Sb with SbI3 in tetrahydrofuran (THF) gives [SbI3(SbMe3)(THF)]2 ( 1 ). [Li(THF)4]2[Bi2Cl8(THF)2] ( 2 ) is formed by reaction of LiCl and BiCl3 in tetrahydrofuran. The structures of ( 1 ) and ( 2 ) have been determined by X-ray diffractometry. Both structures contain centrosymmetric dimers with the geometry of edge sharing octahedra. 相似文献
2.
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
3.
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
4.
Synthesis and Molecular Structure of [Li(THF)4][{(CO)4Mo}2(μ-PPh2)(μ-PPh2PPh2)]: The First Compound with an 1,3-Dimetalla-cyclopentaphosphane Ring [Mo(CO)4(NBD)] (NBD = norbornadiene) reacts with LiPPh2 and PPh2PPh2 in THF at –80 °C to give [Li(THF)4][{(CO)4Mo}2(μ-PPh2)(μ-PPh2PPh2)] ( 1 ). 1 exhibits an A2X coupling pattern in the 31P NMR spectrum. A crystal structure determination showed the presence of bridging phosphanido (PPh2) and diphosphane ligands (PPh2PPh2). The central Mo2P3 five-membered ring adopts a half-chair conformation and thus resembles an inorganic cyclopentane. 相似文献
5.
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
6.
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
7.
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
8.
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
9.
Syntheses and Crystal Structures of the Rare-Earth Complexes [LaI2(THF)5]+I3?, [SmCl3(THF)4], [ErCl2(THF)5]+ [ErCl4(THF)2]?, [ErCl3(DME)2], and [Na(18-Crown-6)(THF)2]+[YbBr4(THF)2]? [LaI2(THF)5]+I3? ( 1 ) is obtained as red crystals from lanthanum powder and 1,2-diiodoethane in THF on exposure to light. Space group Pbcn, Z = 4, lattice dimensions at ?83°C: a = 1264.9, b = 2218.9, c = 1199.1 pm, R = 0.031. The lanthanum atom of the cation of 1 is coordinated with iodine atoms in the axial positions in a pentagonal-bipyramidal way. [SmCl3(THF)4] ( 2 ) originates as colourless crystals on heating SmCl3 with excess THF in the presence of Me3SiNPEt3. Space group P21/c, Z = 8, lattice dimensions at ?50°C: a = 3092.7, b = 826.2, c = 1758.3 pm, β = 93.85°, R = 0.054. Just like the known sample that crystallizes within the space group F2dd, 2 forms monomeric molecules in which the samarium atom is coordinated with two chlorine atoms in the axial positions in a distorted pentagonal-bipyramidal way. [ErCl2(THF)5]+[ErCl4(THF)2]? ( 3 ). Pale pink single crystals of 3 were prepared according to the described method by reaction of erbium powder with trimethylchlorosilane and methanol in THF. Space group C2/c, Z = 4, lattice dimensions at ?50°C: a = 1246.3, b = 1145.7, c = 2726.0 pm, β = 91.293°, R = 0.036. The erbium atom of the cation of 3 has a pentagonal-bipyramidal coordination with the chlorine atoms in the axial positions. Within the anion the THF molecules are in trans-arrangement of the octahedrally coordinated erbium atom. [ErC13(DME)2] ( 4 ) originates as pink single crystals from 3 with excess boiling 1,2-dimethoxyethane. Space group P21/c, Z = 4, lattice dimensions at ?50°C: a = 1137.2, b = 886.5, c = 1561.1 pm, β = 104.746°, R = 0.032. 4 forms monomeric molecules in which the erbium atom has a pentagonal-bipyramidal surrounding with two chlorine atoms in the axial positions. [Na(18-Krone-6)(THF)2]+ [YbBr4(THF)2]? ( 5 ) is formed as by-product by the reaction of YbBr3 with NaN(SiMe3)2 in THF in the presence-of 18-crown-6 forming colourless crystals. Space group P1 , Z = 1, lattice dimensions at ?70°C: a = 934.6, b = 988.9, c = 1208.0 pm, α = 73.82°, β = 72.98°, γ = 76.89°, R = 0.029. 5 contains isolated [YbBr4(THF)2]?ions, in which the THF molecules are arranged in trans-position. 相似文献
10.
Preparation and Vibrational Spectra of Dichloro and Dibromodithiophosphate. Crystal Structures of [PPh3Me][PS2Cl2] and [PPh4][PS2Br2] Dichloro and dibromodithiophosphates [Cat+][PS2X2?] with a large organic cation can be obtained from P4S10, CatX and HX in CH2Cl2 (Cat+ = PPh4+, PPh3Me+; X = Cl, Br). The vibrational spectra (i.r. and Raman) of the [PS2X2]? ions are reported and discussed; force constants were calculated. The crystal structures of [PPh3Me][PS2Cl2] and [PPh4][PS2Br2] were determined and refined with X-ray diffraction data. In both cases, simple anions [PS2X2]? are present. [PPh3Me][PS2Cl2]: orthorhombic, space group P212121, a = 1089, b = 1334, c = 1476 pm, Z = 4, refinement to a residual index R = 0.046 for 1116 reflexions; the structure is isotopic with [PPh3Me][VO2Cl2]. [PPh4][PS2Br2]: tetragonal space group I4 , a = 1301, c = 721 pm, Z = 2, refinement to R = 0.065 for 357 reflexions; the structure is isotypic with [AsPh4][FeCl4] with [PS2Br2]? ions occupying positions of 4 -symmetry with statistical orientation (statistical superposition of Br and S positions). 相似文献
11.
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
12.
Syntheses and Structure Elucidations of Novel (Ironcarbonyl)zinc and ‐cadmium Chloride Derivatives Reactions of zinc/cadmium chloride with Na2[Fe(CO)4] lead to a number of new (iron carbonyl)zinc/cadmium chlorides, wherein the reaction course depends on the used solvent used. In the reaction of ZnCl2 with Na2[Fe(CO)4], three new substances can be prepared. The compound [Zn2Cl2Fe(CO)4(THF)2] ( 1 ), which consists of neutral polymeres, is formed in THF, the ionic compound [Na(DME)3][Zn2Cl3Fe(CO)4] ( 2 ) forms in DME, and from a mixture of THF and TMEDA the compound [Zn2Cl2Fe(CO)4(TMEDA)2] ( 3 ) is obtained as a monomere. Also by using CdCl2, the reaction with Na2[Fe(CO)4] in THF leads to the polymeric compound ([(Cd4Cl6)Fe(CO)4(THF)5] ( 4 )). Carrying out the reaction in a mixture of toluene and DME leads to the formation of the ionic compound [Na(DME)3]2[Cd6{Fe(CO)4}6Cl2(DME)2] ( 5 ) in which an annular dianion consisting of twelve metal atoms is found. From an aqueous solution and subsequent work‐up in THF, the compound [Fe(THF)4(H2O)2][Cd8{Fe(CO)4}4Cl9(THF)6]2 ( 6 ) can be prepared which contains an cluster anion that is built of anellated six membered rings. 相似文献
13.
Two [MoOCl3(THF)2] molecules are used for detachment of two Cl atoms from [MgCl2(THF)2]. In such reaction a green crystalline salt [Mg(THF)6][MoOCl4THF]2 IV is formed. Compound IV reacts further with 3 equivalents of bis(tetrahydrofuran)magnesium dichloride, yielding a green ionic [Mg2(m?-Cl)3(THF)6][MoOCl4THF] compound V . Compound IV and V vary only in a structure of cation what indicated that the tri-m?-chlorohexakis(tetrahydrofuran)dimagnesium(II) cation in V is really formed in reaction between [Mg(THF)6]2+ cation and [MgCl2(THF)2]. The crystal structure of compounds IV and V has been solved by X-ray diffraction method. The [Mg(THF)6]2+ cation forms the tetragonally distorted octahedron with the magnesium atom in the symmetry centre. In homobimetallic di-octahedral [Mg2(m?-Cl)3(THF)6]+ cation the magnesium atoms are surrounded by three bridging chlorine atoms and three THF molecules. The structures of [MoOCl4THF]? in IV and V are similar. In those anions the molybdenum atom is hexacoordinated with four chlorine atoms in equatorial plane. 相似文献
14.
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
15.
The betain‐like compound S2CC(PPh3)2 ( 1 ), which is obtained from CS2 and the double ylide C(PPh3)2, reacts with [Co2(CO)8] and [Mn2(CO)10] in THF to afford the salt‐like complexes [Co{S2CC(PPh3)2}3][Co(CO)4]3 ( 2 ) and [(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5] ( 3 ), respectively, in good yields. At both d6 cations 1 acts as a chelating ligand. Disproportionation reactions from formal Co0 into CoIII and Co?I and from Mn0 into MnI and Mn?I occurred with the removal of four or one carbonyl groups, respectively. The crystal structures of 2· 5.5THF and 3· 2THF are reported, which show a shortening of the C–C bond in the ligand upon complex formation. The compounds are further characterized by 31P NMR and IR spectroscopy. 相似文献
16.
New Amido and Imido Bridged Complexes of Copper – Syntheses and Structures of [{Li(OEt2)}2][Cu(NPh2)3], [ClCuN(SnMe3)3], [{CuN(SnMe3)2}4], [Cu16(NH2tBu)12Cl16], [{CuNHtBu}8], [Li(dme)3][Cu6(NHMes)3(NMes)2], [PPh3(C6H4)CuNHMes], [{[Li(dme)][Cu(NHMes)(NHPh)]}2], and [{Li(dme)3}3][Li(dme)2][Cu12(NPh)8] The reactions of stannylated and lithiated amines with coppersalts (halogenides, thiocyanates) lead to amido and imido bridged complexes which contain one to twelve metal atoms. [{Li(OEt2)}2][Cu(NPh2)3] ( 1 ) results from the reaction of CuCl with LiNPh2 in the presence of trimethylphosphine. With N(SnMe3)3, CuCl reacts to the donor‐acceptor complex [ClCuN(SnMe3)3] ( 2 ) that is transformed into the tetrameric complex [{CuN(SnMe3)2}4] ( 3 ) by thermolysis. 3 can also be obtained by the reaction of LiN(SnMe3)2 with Cu(SCN)2. While terminally bound in 1 , the amido ligand is μ2‐bridging between copper atoms in compound 3 . The influence of the alkyl amide's leaving group can be seen from a comparison of the reactivity of Me3SnNHtBu and LiNHtBu, respectively. With Me3SnNHtBu, CuCl2 forms the polymeric compound [Cu16(NH2tBu)12Cl16] ( 4 ) whereas in the case of LiNHtBu with both CuCl and CuSCN, the complex [{CuNHtBu}8] ( 5 ) is obtained. The latter contains two planar Cu4N4‐rings similar to those in 3 . If a mesityl group is introduced at the lithium amide, different products are accessible. Both, CuBr and CuSCN, lead to the formation of [Li(dme)3][Cu6(NHMes)3(NMes)2] ( 6 ) whose anion consists of a prismatic copper core with μ2‐bridging amido and μ3‐bridging imido ligands. In the presence of PPh4Cl, a mixture of Cu(SCN)2 and LiNHMes enables an ortho‐metallation reaction that produces [PPh3(C6H4)CuNHMes] ( 7 ). From the reaction of CuSCN with LiNHMes and LiNHPh either the dimeric complex [{[Li(dme)][Cu(NHMes)(NHPh)]}2] ( 8 ) or the cluster [{Li(dme)3}3][Li(dme)2][Cu12(NPh)8] ( 9 ) results. The anion in 9 exhibits a cubo‐octahedron of copper atoms μ3‐bridged by (NPh)2–‐ligands. The solid state structures of compounds 1 – 9 have been determined by single crystal X‐ray diffraction. 相似文献
17.
Birgit Siewert Gertraude Koellner Karin Ruhlandt-Senge Fritjof Schmock Ulrich Müller 《无机化学与普通化学杂志》1991,593(1):160-168
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
18.
The Reaction of Ytterbium with N‐iodo‐triphenylphosphaneimine. Crystal Structures of [Yb2I(THF)2(NPPh3)4] · 2 THF, [YbI2(HNPPh3)(DME)2], and [{YbI2(DME)2}2(μ‐DME)] When treated with ultrasound, the reaction of ytterbium powder with INPPh3 in tetrahydrofuran leads to [YbI2(THF)4] and to the mixed‐valence phosphoraneiminato complex [Yb2I(THF)2(NPPh3)4] · 2 THF ( 1 ), which forms red single‐crystals. In the analogous reaction in 1,2‐dimethoxyethane (DME) only the ytterbium(II) iodide solvates [YbI2(HNPPh3)(DME)2] ( 2 ) and [{YbI2(DME)2}2 · (μ‐DME)] ( 3 ) can be isolated, which form yellow single crystals. All compounds were characterized by crystal structure analyses. 1 : Space group P1, Z = 2, lattice dimensions at –80 °C: a = 1337.6(5), b = 1389.6(5), c = 2244.2(17) pm; α = 86.11(7)°, β = 88.06(7)°, γ = 88.63(4)°; R = 0.0759. In 1 the two ytterbium atoms are connected via the N atoms of two phosphoraneiminato groups (NPPh3–) to form a planar Yb2N2 four‐membered ring. The structure can also be described as an ion pair consisting of [YbI(THF)2]+ and [Yb(NPPh3)4]–. 2 : Space group P21, Z = 2, lattice dimensions at –80 °C: a = 811.9(1), b = 1114.0(1), c = 1741.3(1) pm; β = 95.458(5)°; R = 0.0246. 2 forms molecules in which the ytterbium atom is coordinated in a pentagonal‐bipyramidal fashion with the iodine atoms in the axial positions. The O atoms of the two DME‐chelates and the N atom of the phosphaneimine ligand HNPPh3 are in the equatorial positions. 3 : Space group P1, Z = 2, lattice dimensions at –70 °C: a = 817.5(1), b = 1047.7(1), c = 1115.5(2) pm; α = 90.179(10)°, β = 97.543(15)°, γ = 91.087(12)°; R = 0.0317. 3 has a dimeric molecular structure, in which the two fragments {YbI2(DME)2} are connected centrosymmetrically via a μ‐DME bridge. As in 2 , the ytterbium atoms are coordinated in a pentagonal‐bipyramidal fashion with the iodine atoms in the axial positions, as well as with the two DME chelates and with one O atom each of the μ‐DME ligand in the equatorial positions. 相似文献
19.
C. Lau A. Dietrich M. Plate P. Dierkes B. Neumüller S. Wocadlo W. Massa K. Harms K. Dehnicke 《无机化学与普通化学杂志》2003,629(3):473-478
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
20.
Synthesis and Crystal Structure of the Complexes [(n‐Bu)4N]2[{(THF)Cl4Re≡N}2PdCl2], [Ph4P]2[(THF)Cl4Re≡N‐PdCl(μ‐Cl)]2 and [(n‐Bu)4N]2[Pd3Cl8] The threenuclear complex [(n‐Bu)4N]2[{(THF)Cl4Re≡N}2 PdCl2] ( 1 ) is obtained in THF by the reaction of PdCl2(NCC6H5)2 with [(n‐Bu)4N][ReNCl4] in the molar ration 1:2. It forms orange crystals with the composition 1· THF crystallizing in the monoclinic space group C2/c with a = 2973.3(2); b = 1486.63(7); c = 1662.67(8)pm; β = 120.036(5)° and Z = 4. If the reaction is carried out with PdCl2 instead of PdCl2(NCC6H5)2, orange crystals of hitherto unknown [(n‐Bu)4N]2[Pd3Cl8] ( 3 ) are obtained besides some crystals of 1· THF. 3 crystallizes with the space group P1¯ and a = 1141.50(8), b = 1401.2(1), c = 1665.9(1)pm, α = 67.529(8)°, β = 81.960(9)°, γ = 66.813(8)° and Z = 2. In the centrosymmetric complex anion [{(THF)Cl4Re≡N}2PdCl2]2— a linear PdCl2 moiety is connected in trans arrangement with two complex fragments [(THF)Cl4Re≡N]— via asymmetric nitrido bridges Re≡N‐Pd. For Pd(II) thereby results a square‐planar coordination PdCl2N2. The linear nitrido bridges are characterized by distances Re‐N = 163.8(7)pm and Pd‐N = 194.1(7)pm. The crystal structure of 3 contains two symmetry independent, planar complexes [Pd3Cl8]2— with the symmetry 1¯, in which the Pd atoms are connected by slightly asymmetric chloro bridges. By the reaction of equimolar amounts of [Ph4P][ReNCl4] and PdCl2(NCC6H5)2 in THF brown crystals of the heterometallic complex, [Ph4P]2[(THF)Cl4Re≡N‐PdCl(μ‐Cl)]2 ( 2 ) result. 2 crystallizes in the monoclinic space group P21/n with a = 979.55(9); b = 2221.5(1); c = 1523.1(2)pm; β = 100.33(1)° and Z = 2. In the central unit ClPd(μ‐Cl)2PdCl of the centrosymmetric anionic complex [(THF)Cl4Re≡N‐PdCl(μ‐Cl)]22— the coordination of the Pd atoms is completed by two nitrido bridges Re≡N‐Pd to nitrido complex fragments [(THF)Cl4Re≡N]— forming a square‐planar arrangement for Pd(II). The distances in the linear nitrido bridges are Re‐N = 163.8(9)pm and Pd‐N = 191.5(9)pm. 相似文献