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1.
Structure and Properties of the Hydridomethyltetrafluorophosphate Anion, [CH3PF4H] Methyltrifluorphosphorane reacts with strong fluoride donors like CsF, (CH3)4NF and (CH3)4PF with formation of the corresponding hydridomethyltetrafluorophosphates. The salts are characterized by NMR, IR and Raman spectroscopy. The experimental results show that only the trans isomer is formed. For both isomers theoretical calculations (B3LYP/6‐31+G* and RHF/6‐31+G*) were carried out. The difference for the Gibbs free energy between the isomers was calculated to be 35.4 kJ/mol (B3LYP/6‐31+G*). The RHF/6‐31+G* calculation yields, for the almost octahedral trans isomer, bond distances of r(PF) = 167 pm, r(PC) = 184.5 pm and r(PH) = 138.1 pm.  相似文献   

2.
Structure and Properties of Methyltrifluorophosphorane CH3PHF33 Methyldichlorophosphane reacts with three equivalents of HF under formation of Methyltrifluorophosphorane, which is characterized by mass, NMR, and vibrational spectroscopy. The ab intio calculation (HF/6‐31+G*) yields a distorted trigonal bipyramidal structure for CH3PF3H. The methyl group (r P—C = 180.2 pm), the hydrogen (r P—H = 137.1 pm) and one fluorine atom (r P—Feq = 155.8 pm) are located at equatorial positions. The P—Fax‐distance is 163.4 pm. The Lewis‐amphoteric properties are shown by reactions with CsF, [(CH3)4]NF and AsF5.  相似文献   

3.
Colourless, lath‐shaped single crystals of Cs2[B12I12] · 2 CH3CN (monoclinic, C2/m; a = 1550.3(2), b = 1273.2(1), c = 1051.5(1) pm, β = 120.97(1)°; Z = 2) are obtained by the reaction of Cs2[B12H12] with an excess of I2 and ICl (molar ratio: 1 : 2) in methylene iodide (CH2I2) at 180 °C (8 h) and recrystallization of the crude product from acetonitrile (CH3CN). The crystal structure contains quasi‐icosahedral [B12I12]2– anions (d(B–B) = 176–182 pm, d(B–I) = 211–218 pm) which arrange in a cubic closest‐packed fashion. All octahedral interstices are filled with centrosymmetric dimer‐cations {[Cs(N≡C–CH3)]2}2+ containing a diamond‐shaped four‐membered (Cs–N–Cs–N) ring of Cs+ cations and nitrogen atoms of the solvating acetonitrile molecules (d(Cs–N) = 321 pm, 2 ×). The cesium cations themselves actually reside in the distorted tetrahedral voids of the cubic [B12I12]2– packing (d(Cs–I) = 402–461 pm, 10 ×) if one ignores the solvent particles.  相似文献   

4.
Nitriles react with PF5 and also with AsF5, SbF5 forming 1:1-adducts. Using C2Cl3F3 as a solvent is of advantage for this reaction. PF5·CH3CN and [N(C2H5)4]SH give [N(C2H5)4][P2S2F8] with a sulfur double bridge and hexafluorophosphate in acetonitrile [1]. In case of AsF5·CH3CN a salt with the anion [AsF5NHCSCH3]? has been isolated [2]. Following products have been confirmed in a reaction mixture of PF5·CH3CN and SH? in acetonitrile by NMR (31P and 19F): [PF6]?, [F5PSPF5]2?,
, F4PSH, F3PS, HPS2F2, [PS2F2]?, [F5PNC(SH)CH3]?, [F5PNHCSCH3]?, [F5PSH]?. With a ratio PF5·CH3CN: SH? = 2:1 the S-bridge-complexes are prefered whereas in case of a ratio 1:1 the non-bridged P-complexes are the main products.  相似文献   

5.
The Syntheses and Vibrational Spectra of the Homoleptic Metal Acetonitrile Cations [Au(NCCH3)2]+, [Pd(NCCH3)4]2+, [Pt(NCCH3)4]2+, and the Adduct CH3CN · SbF5. The Crystal and Molecular Structures of [M(NCCH3)4][SbF6]2 · CH3CN, M = Pd or Pt Solvolyses of the homoleptic metal carbonyl salts [M(CO)4][Sb2F11]2, M = Pd or Pt, in acetonitrile leads at 50 °C both to complete ligand exchange for the cations as well as to a conversion of the di-octahedral anion [Sb2F11] into [SbF6] and the molecular adduct CH3CN · SbF5 according to: [M(CO)4][Sb2F11]2 + 7 CH3CN → [M(NCCH3)4][SbF6]2 · CH3CN + 2 CH3CN · SbF5 + 4 CO M = Pd, Pt The monosolvated [M(NCCH3)4][SbF6]2 · CH3CN are obtained as single crystals from solution and are structurally characterized by single crystal x-ray diffraction. Both salts are isostructural. The cations are square planar but the N–C–C-sceletial groups of the ligands depart slightly from linearity. The new acetonitrile complexes as well as [Au(NCCH3)2][SbF6] and the adduct CH3CN · SbF5 are completely characterized by vibrational spectroscopy.  相似文献   

6.
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   

7.
The Reactions of M[BF4] (M = Li, K) and (C2H5)2O·BF3 with (CH3)3SiCN. Formation of M[BFx(CN)4—x] (M = Li, K; x = 1, 2) and (CH3)3SiNCBFx(CN)3—x, (x = 0, 1) The reaction of M[BF4] (M = Li, K) with (CH3)3SiCN leads selectively, depending on the reaction time and temperature, to the mixed cyanofluoroborates M[BFx(CN)4—x] (x = 1, 2; M = Li, K). By using (C2H5)2O·BF3 the synthesis yields the compounds (CH3)3SiNCBFx(CN)3—x x = 0, 1. The products are characterized by vibrational and NMR‐spectroscopy, as well as by X‐ray diffraction of single‐crystals: Li[BF2(CN)2]·2Me3SiCN Cmc21, a = 24.0851(5), b = 12.8829(3), c = 18.9139(5) Å V = 5868.7(2) Å3, Z = 12, R1 = 4.7%; K[BF2(CN)2] P41212, a = 13.1596(3), c = 38.4183(8) Å, V = 6653.1(3) Å3, Z = 48, R1 = 2.5%; K[BF(CN)3] P1¯, a = 6.519(1), b = 7.319(1), c = 7.633(2) Å, α = 68.02(3), β = 74.70(3), γ = 89.09(3)°, V = 324.3(1) Å3, Z = 2, R1 = 3.6%; Me3SiNCBF(CN)2 Pbca, a = 9.1838(6), b = 13.3094(8), c = 16.840(1) Å, V = 2058.4(2) Å3, Z = 8, R1 = 4.4%  相似文献   

8.
In(C6F5)3 · CH3CN and In(C6F5)3 · glyme were synthesized from InCl3 and Cd(C6F5)2 in CH3CN or glyme in 43% and 35% yield, respectively. Replacement of CH3CN or (C2H5)2O by DMAP yielded the corresponding 1 : 1-adduct. [PNP][In(C6F5)4] was best prepared from the corresponding cesium salt which was best synthesized from the reaction of stoichiometric amounts of In(C6F5)3 · CH3CN, (CH3)3 SiC6F5 and CsF in good yield. [PNP][In(C6F5)4] crystallizes in the triclinic space group P 1, a = 1104.9(4) pm, b = 1442.4(6) pm, c = 1833.8(8) pm, α = 110.87(2)°, β = 92.04(3)°, γ = 96.55(3)°, Z = 2.  相似文献   

9.
Single crystals of [Be33‐O)3(MeCN)6{Be(MeCN)3}3](I)6·4CH3CN ( 1 ·4CH3CN) were obtained in low yield by the reaction of beryllium powder with iodine in acetonitrile suspension, which probably result from traces of beryllium oxide containing the applied beryllium metal. The compound 1 ·4CH3CN forms moisture sensitive, colourless crystal needles, which were characterized by IR spectroscopy and X‐ray diffraction (Space group Pnma, Z = 4, lattice dimensions at 100(2) K: a = 2317.4(1), b = 2491.4(1), c = 1190.6(1) pm, R1 = 0.0315). The hexaiodide complex cation 1 6+consists of a cyclo‐Be3O3 core with slightly distorted chair conformation, stabilized by coordination of two acetonitrile ligands at each of the beryllium atoms and by a {Be(CH3CN)3}2+ cation at each of the oxygen atoms. This unique coordination behaviour results in coplanar OBe3 units with short Be–O distances of 155.0 pm and 153.6 pm on average of bond lengths within the cyclo‐Be3O3 unit and of the peripheric BeO bonds, respectively. Exposure of compound 1 ·4CH3CN to moist air leads to small orange crystal plates of [Be(H2O)4]I2·2CH3CN ( 3 ·2CH3CN). According to the crystal structure determination (Space group C2/c, Z = 4, lattice dimensions at 100(2) K: a = 1220.7(1), b = 735.0(1), c = 1608.5(1) pm, β = 97.97(1)°, R1 = 0.0394), all hydrogen atoms of the dication [Be(H2O)4]2+ are involved to form O–H ··· N and O–H ··· I hydrogen bonds with the acetonitrile molecules and the iodide ions, respectively. Quantum chemical calculations (B3LYP/6‐311+G**) at the model [Be33‐O)3(HCN)6{Be(HCN)3}3]6+ show that chair and boat conformation are stable and that the distorted chair conformation is stabilized by packing effects.  相似文献   

10.
Synthesis, Vibrational Spectra, and Crystal Structures of the Nitrato Argentates (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN and (Ph4P)[Ag2(NO3)3] Tetraphenylphosphonium bromide reacts in acetonitril suspension with excess silver nitrate to give (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN ( 1 ), whereas (Ph4P)[Ag2(NO3)3] ( 2 ) is obtained in a long‐time reaction from (Ph4P)Br and excess AgNO3 in dichloromethane suspension. Both complexes were characterized by vibrational spectroscopy (IR, Raman) and by single crystal structure determinations. 1 : Space group P21/c, Z = 4, lattice dimensions at 193 K: a = 1781.5(3), b = 724.8(1), c = 2224.2(3) pm, β = 96.83(1)°, R1 = 0.0348. 1 contains isolated complex units [Ag(NO3)2(CH3CN)]?, in which the silver atom is coordinated by the chelating nitrate groups and by the nitrogen atom of the solvated CH3CN molecule with a short Ag—N distance of 220.7(4) pm. 2 : Space group I2, Z = 4, lattice dimensions at 193 K: a = 1753.4(4), b = 701.7(1), c = 2105.5(4) pm, R1 = 0.072. In the polymeric anions [Ag2(NO3)3]? each silver atom is coordinated in a chelating manner by one nitrate group and by two oxygen atoms of two bridging nitrate ions. In addition, each silver atom forms a weak π‐bonding contact with a phenyl group of the (Ph4P)+ ions with shortest Ag···C separations of 266 and 299 pm, respectively, indicating a (4+1) coordination of silver atoms.  相似文献   

11.
The systematic study of the reaction of M[PF6] salts and Me3SiCN led to a synthetic method for the synthesis and isolation of a series of salts containing the unprecedented [PF2(CN)4]? ion in good yields. The reaction temperature, pressure, and stoichiometry were optimized. The crystal structures of M[PF2(CN)4] (M=[nBu4N]+, Ag+, K+, Li+, H5O2+) were determined. X‐ray crystallography showed the exclusive formation of the cis isomer in accord with 31P and 19F solution NMR spectroscopy data. Starting with the K[PF2(CN)4] the room temperature ionic liquid EMIm[PF2(CN)4] was prepared exhibiting a rather low viscosity.  相似文献   

12.
Chromium Hexacyano Complexes: The Crystal Structures of the Cyano Elpasolites (NMe4)2ACr(CN)6 (A = K, Cs) and of the Cubic Barium Compound Ba3[Cr(CN)6]2 · 20 H2O The crystal structures of the cyano elpasolites (NMe4)2KCr(CN)6 (a = 1527.3(1), b = 888.1(1), c = 1539.0(1) pm, β = 109.92(1)°; C2/c, Z = 4) and (NMe4)2CsCr(CN)6 (a = 1278.9(1) pm; Fm3m, Z = 4), as well as of the cubic compound Ba3[Cr(CN)6]2 · 20 H2O (a = 1631.0(1) pm; Im3m, Z = 4) were determined by X‐ray methods with single crystals. Reasons for the enlarged distances within the [Cr(CN)6]3–‐octahedron of the K compound (Cr–C: 209.3 pm) compared to the observations within both cubic complexes (206.1 resp. 206.9 pm) are discussed in context with the tolerance factors of cyano elpasolites. As is the case there concerning the cyano bridges Cr–CN–A towards the alkali ions the novel structure type of the barium compound, too, exhibits nearly linear bridging towards Ba. It contributes, however, only four N ligands to the ninefold [BaN4O5] coordination; part of the aqua ligands show disorder (Ba–N: 287.5, Ba–O: 281/293 pm).  相似文献   

13.
Synthesis and Crystal Structure of the Adducts [DB-18C6] · CH3CN · CH3CSOH and [DC-18C6](CH3CSOH)2 as well as of the Salt-like Compounds [Cs(B-15C5)2]CH3CSS and [Cs(DB-18C6)]2S5(DMF)21) The reaction products of crown ethers, cesium, and sulfur in aprotic solvents like acetonitrile and dimethylformamide strongly depend on the reaction conditions. Using CH3CN as a solvent, sometimes neutral host-guest adducts crystallize only, e.g., [dibenzo-18C6] · CH3CN · CH3CSOH (monoclinic, S. G. P21/c, Z = 4, a = 9.73(1) Å, b = 22.03(1) Å, c = 11.86(1) Å, β = 91.8(1)°) or [dicyclohexyl-18C6](CH3CSOH)2 (monoclinic, S. G. P21/n, Z = 2, a = 7.75(1) Å, b = 10.32(1) Å, c = 17.73(1) Å, β = 95.7(1)°). The monothioacetic acid, CH3CSOH, must be regarded as the first product of the hydrolysis of CH3CN. Furthermore, another product of this kind of hydrolysis, CH3CSSH, is obtained too. Therefore, we also obtain the salt-like compound [Cs(benzo-15C5)2]CH3CSS (monoclinic, S. G. C2/c, Z = 4, a = 16.05(1) Å, b = 16.73(1) Å, c = 13.11(1) Å, β = 106.3(1)°). If the solvent DMF is used, the pentasulfide [Cs(dibenzo-18C6)]2S5(DMF)2 crystallizes (monoclinic, S. G. P21/n, Z = 4, a = 14.79(1) Å, b = 14.24(1) Å, c = 25.74(1) Å, β = 92.7(1°. The S52? anions show the cis-conformation.  相似文献   

14.
Crystal Structures of Octacyanomolybdates(IV). IV Dodecahedral [Mo(CN)8] Coordination of the Cyano‐Bridged Cobalt and Nickel Ammin Complexes MII2(NH3)8[Mo(CN)8] · 1.5 H2O (MII = Co, Ni) and Ni2(NH3)9[Mo(CN)8] · 2 H2O At single crystals of the hydrated cyano complexes Co2(NH3)8[Mo(CN)8] · 1.5 H2O (a = 910.0(4), b = 1671(2), c = 1501(1) pm, β = 93.76(6)°) and Ni2(NH3)8[Mo(CN)8] · 1.5 H2O (a = 899.9(9), b = 1654.7(4), c = 1488(1) pm, β = 94.01°), isostructurally crystallizing in space group P21/c, Z = 4, and of trigonal Ni2(NH3)9[Mo(CN)8] · 2 H2O (a = 955.1(1), c = 2326.7(7) pm, P31, Z = 3), X‐ray structure determinations were performed at 168 resp. 153 K. The [Mo(CN)8]4– groups of the three compounds, prepared at about 275 K and easily decomposing, show but slightly distorted dodecahedral coordination (mean distances Mo–C: 216.3, 215.4 and 216.1 pm). Within the monoclinic complexes the anions twodimensionally form cyano bridges to the ammin cations [M(NH3)4]2+ and are connected with the resulting [MN6] octahedra (Co–N: 215.1 pm, Ni–N: 209.8 pm) into strongly puckered layers. The trigonal complex exhibits a chain structure, as one [Ni(NH3)5]2+ cation is only bound as terminal octahedron (Ni–N: 212.0 pm). Details and the influence of hydrogen bridges are discussed.  相似文献   

15.
Preparation, Spectroscopic Characterization and Crystal Structures of Mercury(II)‐bis(tetracyanoborate) Hg[B(CN)4]2 and Dimercury(I)‐bis(tetracyanoborate) Hg2[B(CN)4]2 Hg[B(CN)4]2 ( 1 ) is synthesised by the reaction between Hg(NO3)2 and K[B(CN)4]2. In a comproportionation reaction of 1 with elemental mercury the corresponding mercury(I) salt Hg2[B(CN)4]2 ( 2 ) is obtained. The compounds were characterised by vibrational‐ and NMR‐spectroscopy, and their crystal structures were determined. Hg[B(CN)4]2 crystallizes in the trigonal system in the space group P3¯m1 with a = 781.75(3) pm, c = 601.68(2) pm, V = 318.44(2)Å3, and one formula unit per unit cell. For Hg2[B(CN)4]2 an orthorhombic unit cell with a = 568.9(1) pm, b = 3280.9(7) pm, c = 601.68(2) pm, V = 1389.6(5)Å, and Z = 4 is observed.  相似文献   

16.
Contributions to the Chemistry of Organo Transition Metal Compounds. 55. Preparation and Properties of Niobocenium and Tantalocenium Salts — Crystal and Molecular Structure of [(C5H5)2NbCl2][BF4] · CH3CN Niobocenium and tantalocenium compounds of the type [(C5H5)2MCl2]X (X = BF4, PBh4, PF6) were synthesized from the metallocene dichlorides and ferricenium salts, [(C5H5)2Fe]X, in methylene dichloride or tetrahydrofuran. With acetonitrile as solvent [(C5H5)2MCl2]X · CH3CN complexes are formed. Stable methyl compounds of the type [(C5H5)2M(CH3)2]X were obtained, when (C5H5)2Ta(CH3)2 is oxidized by means of ferricenium salts. The new complexes were characterized by elemental analysis, i. r., and 1H n.m.r. spectra. The structure of [(C5H5)2NbCl2][BF4] · CH3CN has been determined by X-ray structure analysis. The compound crystallizes in the orthorhombic space group Cmcm with a = 8.324(12), b = 19.581(13), c = 9,563(8) Å and Z = 4. The coordination geometry of the Nb atom is tetrahedrally.  相似文献   

17.
On the Crystal Structures of the Cyano Complexes [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O, and [Cu(en)2][Ni(CN)4] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH3)6][Fe(CN)6] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH3)6][Co(CN)6] type structure. [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H2O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)2][Ni(CN)4] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.  相似文献   

18.
Phosphorane Iminato Complexes of Antimony. The Crystal Structures of [Sb2Cl5(NPMe3)2][SbCl6] · CH3CN and [SbCl(NPPh3)]2[SbCl6]2 · 6 CH3CN The title compounds are formed by reaction of antimony pentachloride in acetonitrile solution with the phosphorane iminato complexes SbCl2(NPMe3) and SbCl2(NPPh3), respectively, which themselves are synthesized by reaction of antimony trichloride with Me3SiNPR3 (R = Me, Ph). The complexionic compounds are characterized by 121Sb Mössbauer spectroscopy and by crystal structure determinations. [Sb2Cl5(NPMe3)2][SbCl6] · CH3CN: Space group P41, Z = 4, 3 698 observed unique reflections, R = 0.022. Lattice dimensions at ?60°C: a = b = 1 056.0(1), c = 2 709.6(2) pm. The structure consists of SbCl6? ions and cations [Sb2Cl5(NPMe3)2(CH3CN)]+, in which one SbIII atom and one SbV atom are bridged by the N atoms of the phosphorane iminato ligands. [SbCl(NPPh3)]2[SbCl6]2 · 6 CH3CN: Space group P1 , Z = 2, 5 958 observed unique reflections, R = 0.033. Lattice dimensions at ?60°C: a = 989.4(11), b = 1 273(1), c = 1 396(1) pm, α = 78.33(7), β = 77.27(8)°, γ = 86.62(8)°. The structure consists of SbCl6? ions and centrosymmetric cations [SbCl(NPPh3)(CH3CN)2]22+, in which the antimony atoms are bridged by the N atoms of the phosphorane iminato ligands.  相似文献   

19.
The reaction of [CpRu(CH3CN)3]PF6 with the bidentate ligands L-L=1,2-bis(diphenylphosphino)ethane, dppe, and (1-diphenylarsino-2-diphenylphosphino)ethane, dpadppe, affords mononuclear or dinuclear complexes of formula [CpRu(η2-L-L)(CH3CN)]PF6, [{CpRu(CH3CN)2}2(μ-η1:1-L-L)](PF6)2 and [{CpRu(CH3CN)}2(μ-η1:1-L-L)2](PF6)2 (L-L=dppe, dpadppe). All of the compounds are characterized by microanalysis and NMR [1H and 31P{1H}] spectroscopy. The crystal structure of [{CpRu(CH3CN)2}2(μ-η1:1-dppe)](PF6)2 has been determined by X-ray diffraction analysis. The complex exhibits a dppe ligand bridging two CpRu(CH3CN)2 fragments.  相似文献   

20.
Synthesis and Structure of K[Au(AuCl)(AuPPh3)8)](PF6)2 Photolysis of a mixture of Ph3PAuCl and Ph3PAuN3 (1 : 3) in toluene/THF yields in the presence of Na2[(C5H5)V(CO)3] the new cluster cation [Au(AuCl)(AuPPh3)8]+. It crystallizes from CH2Cl2 after addition of KPF6 as K[Au(AuCl)(AuPPh3)8](PF6)2 · 4 CH2Cl2. The compound forms a tetragonal structure with the space group P4/n and a = 2552.6(3), c = 1401.1(1) pm, Z = 2. The cluster cations with a spheroidal topology are built up of a centered Au8 crown whose central gold atom in addition binds a AuCl group. The cluster occupies with its center and AuCl group a fourfold axis of the space group. The radial bonds between the central and the peripheral Au atoms are in the range of 263.7 to 268.4 pm, while the distances between the peripheral atoms are longer with 291.7 to 350.9 pm.  相似文献   

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