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Dr. Jörn Bruns M. Sc. David van Gerven Prof. Dr. Thorsten Klüner Prof. Dr. Mathias S. Wickleder 《Angewandte Chemie (International ed. in English)》2016,55(28):8121-8124
For the first time tetravalent palladium is detected, coordinated exclusively by simple oxoanions. Stabilization was achieved by formation of the [Pd(S2O7)3]2? complex in which three chelating disulfate groups surround the metal atom. The salt K2[Pd(S2O7)3] could only be obtained if the reaction of K2[PdCl6] and neat SO3 was performed in the presence of XeF2. 相似文献
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Christian Logemann Daniel Gunzelmann Prof. Dr. Thorsten Klüner Prof. Dr. Jürgen Senker Prof. Dr. Mathias S. Wickleder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(48):15495-15503
The reactions of group 14 tetrachlorides MCl4 (M=Si, Ge, Sn) with oleum (65 % SO3) at elevated temperatures lead to the unique complex ions [M(S2O7)3]2?, which show the central M atoms in coordination with three chelating S2O72? groups. The mean distances M? O within the anions increase from 175.6(2)–177.5(2) pm (M=Si) to 186.4(4)–187.7(4) pm (M=Ge) to 201.9(2)–203.5(2) pm (M=Sn). These distances are reproduced well by DFT calculations. The same calculations show an increasing positive charge for the central M atom in the row Si, Ge, Sn, which can be interpreted as the decreasing covalency of the M? O bonds. For the silicon compound (NH4)2[Si(S2O7)3], 29Si solid‐state NMR measurements have been performed, with the results showing a signal at ?215.5 ppm for (NH4)2[Si(S2O7)3], which is in very good agreement with theoretical estimations. In addition, the vibrational modes within the [MO6] skeleton have been monitored by Raman spectroscopy for selected examples, and are well reproduced by theory. The charge balance for the [M(S2O7)3]2? ions is achieved by monovalent A+ counter ions (A=NH4, Ag), which are implemented in the syntheses in the form of their sulfates. The sizes of the A+ ions, that is, their coordination requirements, cause the crystallographic differences in the crystal structures, although the complex [M(S2O7)3]2? ions remain essentially unaffected with the different A+ ions. Furthermore, the nature of the A+ ions influences the thermal behavior of the compounds, which has been monitored for selected examples by thermogravimetric differential thermal analysis (DTA/TG) and XRD measurements. 相似文献
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Single crystals of trans-[Pd(NO3)2(H2O)2] were obtained, and the crystal structure of this complex, previously obtained for polycrystals, was refined. Crystal data (BRUKER X8APEX diffractometer): a = 4.9973(7) Å, b = 10.5982(14) Å, c = 11.7008(17) Å, V = 619.70(15) Å3, space group Pbca, Z = 4, d calc = 2.856 g/cm3. The structure is composed of neutral complexes with a trans configuration. The square plane environment of the Pd atom is formed by four oxygen atoms (Pd-O(NO3) 1.999(5) Å, Pd-O(H2O) 2.030(5) Å) and completed to a distorted bipyramid by two intramolecular contacts (Pd…O(NO3) 2.926 Å). The shortest hydrogen bonds are O…H 2.72 Å. 相似文献
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Towards Polysulfuric Acids: The Hydrogentrisulfate Anion [HS3O10]− in A[HS3O10] (A=Na,K, Rb)
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Lisa Verena Schindler Prof. Dr. Thorsten Klüner Prof. Dr. Mathias S. Wickleder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(39):13865-13870
The reaction of Na2SO4 and K2SO4 with fuming sulfuric acid (65 % SO3) yielded colorless extremely sensitive crystals of Na[HS3O10] (monoclinic; P21/n (No. 14); Z=4; a=707.36(2), b=1378.56(4), c=848.10(3) pm; β=94.817(1)°; V=824.09(4) ? 106 pm3) and K[HS3O10] (orthorhombic; Pccn (No. 56); Z=4; a=1057.16(3), b=807.81(2), c=897.57(2) pm; V=766.51(3) ? 106 pm3). The analogous rubidium compound Rb[HS3O10] (orthorhombic; Pnma (No. 62); Z=4; a=891.43(3), b=1095.34(4), c=839.37(3) pm; V=819.58(5) ? 106 pm3) originates from the reaction of Rb2CO3 and SO3. All of the different structures contain the hitherto unknown anion [HS3O10]? and are stamped by strong hydrogen bonds linking the anions either to dimers or chains. Theoretical investigations by DFT methods give further insight in the structural characteristics of [HS3O10]?. The preparation of the [HS3O10]? anion can be seen as an important milestone on our way to the still elusive polysulfuric acids. 相似文献
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Jörn Bruns Oliver Niehaus Prof. Dr. Rainer Pöttgen Prof. Dr. Mathias S. Wickleder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(3):811-814
The reaction of (NO2)(CF3SO3) and elemental palladium in oleum (65 % SO3) leads to violet single crystals of Pd(HS2O7)2 (monoclinic, P21/c, Z=2, a=927.80(9), b=682.58(7), c=920.84(9) pm, β=117.756(2)°, wR2=0.0439). In the crystal structure, the Pd2+ ions show an uncommon octahedral coordination of six oxygen atoms belonging to six HS2O7? ions. The linkage of [PdO6] octahedra and the hydrogendisulfate anions leads to a layer structure, and the layers are held together by hydrogen bonds. The unusual coordination of the Pd2+ ions results in an electronic d8 high‐spin configuration, which leads to the paramagnetic behavior of the compound. Moreover, at low temperature, a ferromagnetic ordering was observed with a Curie temperature of 8 K. 相似文献
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Jörn Bruns Sascha Krüger Dr. Matthias Adlung Prof. Dr. Claudia Wickleder Oliver Niehaus Prof. Dr. Rainer Pöttgen Prof. Dr. Thorsten Klüner Jessica Kräuter Prof. Dr. Mathias S. Wickleder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(35):12389-12395
The reaction of Eu2O3 with fuming nitric acid, trifluormethanesulfonic acid, and its anhydride in torch‐sealed glass ampoules at 120 °C gave the europium compound (NO)5[Eu(O3SCF3)8] (orthorhombic, Fddd, Z=16, a=1932.69(4), b=2878.44(7), c=2955.12(7) pm, V=16439.7(7) Å3). The compound exhibits the [Eu(O3SCF3)8]5? anion showing for the first time a lanthanide ion that is exclusively coordinated by eight triflate anions. The anion has been further investigated by DFT calculations, which also allowed clear assignment of the vibrational spectra. Moreover, magnetochemical and luminescence measurements gave additional insight into the properties of this complex. The luminescence spectra revealed that the Eu3+ ions are in a pseudo D4d symmetric environment. 相似文献
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Hebben N Himmel HJ Eickerling G Herrmann C Reiher M Herz V Presnitz M Scherer W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(36):10078-10087
In this article we analyze in detail the electronic properties of the D(3h)-symmetric tris(ethylene) complexes of nickel, palladium, and platinum ([M(C(2)H(4))(3)] M=Ni, Pd, Pt). In the case of [Pd(C(2)H(4))(3)] the analysis is based on new experimental IR and Raman spectra for the matrix-isolated molecules and in all cases on the results of quantum-chemical (DFT) calculations. The experimental spectra collected for [Pd(C(2)H(4))(3)] provide evidence for several previously unobserved vibrational modes, including the in-phase and out-of-phase nu(C-C) and delta(CH(2)) modes, and the in-phase nu(M-C) mode. Special consideration is given to possible inter-ligand interactions. The interaction force constant f(CC,CC) between two C(2)H(4) ligands can be directly estimated from the spectra, and its very small value (0.002 N m(-1)) indicates the absence of any significant inter-ligand interaction. An analysis of the topology of the theoretical electron density distribution, rho(r), and the corresponding Laplacian, nabla(2)rho(r), for [Pd(C(2)H(4))(3)] and its lighter and heavier homologues [Ni(C(2)H(4))(3)] and [Pt(C(2)H(4))(3)], respectively, is in full agreement with the conclusions drawn from the experimental results. The combined experimental and quantum-chemical results provide detailed insights in the electronic properties of these prototypical ethylene complexes. 相似文献
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The hydroxy yttrium hexaborate,Y[B2O3(OH)]3,has been synthesized under mild hydrothermal conditions at 458 K.The crystal structure was solved and refined from single-crystal X-ray diffraction.It adopts a trigonal space group R3c(No.161) with a = 8.3942(4),c = 20.6484(12) ,V = 1260.03(12) 3,YB6H3O12,Mr = 348.79,Z = 6,Dc = 2.758 g/cm3,F(000) = 1008,μ = 7.015 mm-1,R = 0.0321 and wR = 0.0772.Its crystal structure is made up of six-membered rings,alternating three-connected [BO3(OH)] tetrahedra and planar [BO3] trigonal groups,which are interconnected with each other by sharing their common oxygen corners to form a three-dimensional framework structure with six-membered ring channels that are occupied by the yttrium atoms and run along the c axis.FT-IR,Raman,and TG-DTA results are also presented. 相似文献
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Raphael Seelbinder Dr. Nadine R. Goetz Johannes Weber Dr. Rolf Minkwitz Prof. Dr. Andreas J. Kornath Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(3):1026-1032
Sulfurtrioxide reacts with the superacidic solutions XF/SbF5 (X=H, D) to form the corresponding salts [X2SO3F]+[SbF6]?, which are the protonated forms of fluorosulfuric acid. The salts have been characterized by vibrational spectroscopy and a single‐crystal structure analysis. [H2SO3F]+[SbF6]? crystallizes in the monoclinic space group P21/n (no. 14) with four formula units in the unit cell. The crystal structure possesses a distorted tetrahedral O3SF skeleton of the cations, which are linked with two strong hydrogen bridges to [SbF6]? anions and forms a one‐dimensional chain. The crystal structure and the vibrational spectra are compared to the quantum‐chemical‐calculated free [H2SO3F]+ cation. Additionally, an [H2SO3F(HF)2]+ unit was calculated at the RHF/6‐311++G(d,p) level to simulate H???F hydrogen bridges found in the solid state. 相似文献
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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
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Alexander D. Burns Brian O. Patrick Anita E. Lam David Dreisinger 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(7):726-731
Two new solid‐state uranium(IV) sulfate x‐hydrate complexes (where x is the total number of coordinated plus solvent waters), namely catena‐poly[[pentaaquauranium(IV)]‐di‐μ‐sulfato‐κ4O:O′] monohydrate], {[U(SO4)2(H2O)5]·H2O}n, and hexaaquabis(sulfato‐κ2O,O′)uranium(IV) dihydrate, [U(SO4)2(H2O)6]·2H2O, have been synthesized, structurally characterized by single‐crystal X‐ray diffraction and analyzed by vibrational (IR and Raman) spectroscopy. By comparing these structures with those of four other known uranium(IV) sulfate x‐hydrates, the effect of additional coordinated water molecules on their structures has been elucidated. As the number of coordinated water molecules increases, the sulfate bonds are displaced, thus changing the binding mode of the sulfate ligands to the uranium centre. As a result, uranium(IV) sulfate x‐hydrate changes from being fully crosslinked in three dimensions in the anhydrous compound, through sheet and chain linking in the tetra‐ and hexahydrates, to fully unlinked molecules in the octa‐ and nonahydrates. It can be concluded that coordinated waters play an important role in determining the structure and connectivity of UIV sulfate complexes. 相似文献
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Preparation and Crystal Structures of the first Alkalimetall‐hexacarbonato‐oxotetraberyllates: K6[Be4O(CO3)6] · 7 H2O and K6[Be4O(CO3)6] K6[Be4O(CO3)6] · 7 H2O has been prepared by dissolving freshly precipitated Be(OH)2 in an aqueous KHCO3 solution. After enriching the title compound by extraction with ethanol the heptahydrate crystallizes from the organic phase (triklin, P1¯ (No. 2) with a = 951, 01(11), b = 958, 45(12), c = 1601, 7(2) pm, α = 79, 253(13)°, β = 78, 943(12)°, γ = 65, 119(12)°, VEZ = 1290, 6(3)·106 pm3, Z = 2). Thermal decomposition forms rhombohedral crystals of the anhydrous compound (trigonal‐rhombohedric, R3¯ (No. 148) with a = 1416, 42(6), c = 1704, 5(1) pm, VEZ = 2961, 4(3)·106 pm3, Z = 6). 相似文献
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Alkaline Molybdotellurates: Preparation and Crystal Structures of Rb6[TeMo6O24] · 10H2O and Rb6[TeMo6O24] · Te(OH)6 · 6H2O Single crystals of Rb6[TeMo6O24] · 10 H2O and Rb6[TeMo6O24] · Te(OH)6 · 6 H2O, respectively, were grown from aqueous solution. Rb6[TeMo6O24] · 10 H2O possesses the space group P1 . The lattice dimensions are a = 963.40(13), b = 972.56(12), c = 1 056.18(13) pm, α = 97.556(10), β = 113.445(9), γ = 102.075(10)°; Z = 1, 2 860 reflections, 215 parameters refined, Rg = 0.0257. The centrosymmetrical [TeMo6O24]6? anions are stacked parallel to [010]. Rb(2) is coordinated with one exception by water molecules only. Folded chains consisting of [TeMo6O24]6? anions and Rb(2) coordination polyhedra which are linked to pairs represent the prominent structural feature. Rb6[TeMo6O24] · Te(OH)6 · 6 H2O crystallizes monoclinically in the space group C2/c with a = 1 886.4(3), b = 1 000.9(1), c = 2 126.5(3) pm, and β = 115.90(1)°; Z = 4, 3 206 reflections, 240 parameters refined, Rg = 0.0333. It is isostructural in high extent with (NH4)6[TeMo6O24] · Te(OH)6 · 7 H2O. Hydrogen bonds between Te(OH)6 molecules and [TeMo6O24]6? anions establish infinite strands. The [TeMo6O24]6? anions gather around Te(OH)6 providing channel-like voids extending parallel to [001]. 相似文献
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E. I. Voit A. V. Voit A. A. Mashkovskii N. M. Laptash V. Ya. Kavun 《Journal of Structural Chemistry》2006,47(4):642-650
Ammonium oxofluorotungstates, (NH4)2WO2F4 and (NH4)3WO3F3, are characterized by vibration spectroscopy and quantum chemistry methods with the use of NMR 19F and 1H data. It is shown in the approximation of the density-functional theory that in isolated octahedrons [WO2F4]2? and [WO3F3]3? the mutual arrangement of oxygen atoms in cis-position corresponds to the energy minimum. The presence of intraspheric disorder in [WO3F3]3? (unlike [WO2F4]2?) explains the complex character of vibrational spectra of this anion and eliminates existent in the literature differences in their interpretation (between C 2v and C 3v structure variants). Models of intraspheric dynamics of [WO3F3]3? are discussed. 相似文献