Kristall-und molekülstrukturen zweier modifikationen de hexaphenyldigermylsulfids (C6H5)3GeSGe(C6H5)3

en Two differnt crystal modifications of hexaphenyldigermanium sulfide (C₆H₅GeSGe(C₆H₅)₃ (I and II were obtained by crystallization from hot benzene/methanol or form ethanol at 20°C. Single crystal X-ray structural analyses for both I (low temperature data at ?130°C) and II (at 20°C) (I, R = 0.046; II, R = 0.048) were performed. I is monoclinic, P2¹/c, with a = 11.020(3), b = 15.473(3), c 18.606(3) »,π = 106.92(2)°, Z = 4; II is orthorhombic, P2₁2₁2₁, with a = 2.617(2), b = 17.345(3), c = 18.408(3) », Z = 4.The molecules have different conformeric structures with respect to a rotation of the (C₆H₆)₃Ge groups around the Ge bonds with very similar bond lenghts and angles. Bond data for I(II) are: GeS 2.212(1) and 2.261(1) » (2.227(2) and 2.240(2) »); GeC 1.933(4) ? 1.971(4), mean 1.945(5) » (1.931(7)?1.954(7), mean 1.943(4) »); GeSGe 111.2(1)° (110.7(1)°). The Ge bond lenghts are comparable to those in thiogermanates and do not indicate significant π-bond contributions.     

A theoretical study of the structures and inversion barriers of CF3− and SiF3−

The structures and inversion barriers of CF₃^? and SiF₃^? have been calculated using ab initio SCF theory with several different basis sets and limited CI. The highest occupied molecular orbital of planar SiF₃^? is shown to have a₁′ symmetry, rather than the normally expected a₂″ symmetry. The best estimates of the inversion barriers are 119 kcal mol^?1 (CF₃^?) and 82 kcal mol ^?1 (SiF₃^?).     

A novel mononuclear gold(I) complex: Synthesis and x-ray structure of [Au{P(C6H5)3}3][SiF5] · 1.5 CH2Cl2

Tris(triphenylphosphine)gold(I)-pentafluorosilicate(IV) ([Au{P(C₆H₅)₃}₃][SiF₅]) was prepared and the structure was determined by single crystal x-ray diffraction. The complex crystallizes in the triclinic space group P1 (No. 2). The lattice constants are a = 14.634(2) Å, b = 17.180(2) Å, c = 22.212(3) Å, α = 86.48(1)°, β = 78.95(1)°, γ = 83.99(1)°. Number of molecules per cell: Z = 4. The gold atoms are coordinated to three triphenylphosphine ligands to form the trigonal planar cation [Au{P(C₆H₅)₃}₃]⁺. Separated from the cation is the [SiF₅]^? anion which is regular trigonal bipyramidal coordinated. No interactions between the fluorine atoms and the gold atoms were observed.     

Novel ammonium hexafluoroarsenate salts from reaction of (CF3)2NH,CF3N(OCF3)H,CF3N[OCF(CF3)2]H,CF3NHF and SF5NHF with the strong acid HF/ASF5.

Reactions of the fluorinated amines (CF₃)₂NH, CF₃N(OCF₃)H, CF₃N[OCF(CF₃)₂]H, CF₃NHF and SF₅NHF with the strong acid HF/AsF₅ form the corresponding ammonium salts R_f¹R_f²NH₂⁺AsF₆^? and R_fNFH₂⁺ AsF₆^? in high yield. [R_f¹=CF₃, R_f²=CF₃, CF₃O, (CF₃)₂CFO; R_f=CF₃, SF₅] The colorless crystalline solids are stable for prolonged periods at 22°C in sealed FEP containers. They have dissociation pressures at 22°C ranging from ～5 torr (R_fNFH₂⁺ AsF₆^?) to ～50 torr [CF₃N(OCF₃)H₂⁺AsF₆^?]. ¹⁹F NMR and Raman spectroscopy were used to identify the compounds.     

Synthesis and properties of pentamethylmetallocene derivatives Cp*MCp (M = Ru, Fe). Crystal structure of the salt [CpRuC5Me4CH2+OC6H2(NO2)3-]

Photolysis of a solution of Cp*RuCp (1) in CF₃CO₂H generates salt [CpRu(C₅Me₄CH₂)]-(O₂CCF₃)(2 • O₂CCF₃). The reaction of compound 1 with oleum at 20 °C through the intermediate dication [η⁵-(CH₂C₅Me₄)Ru(μ:η⁵,ν⁵-C₅H₄C₅H₅)Ru(C₅Me₄CH₂)-η⁶]²⁺ leads to the triply charged cation η⁷CH₂)₂C₅Me₃Ru(μη⁵,η⁵-C₅H₄C₅H₄)Ru(C₅Me₄CH₂)-η⁶]³⁺. Synthesis of pentamethylmetallocene derivatives CpMC₅Me₄X (M = Ru, Fe; X = CHO, CH₂OH, CH₂An) has been accomplished. The reactions of 1-hydroxymethyl-2,3,4,5-tetramethylruthenocene with acids CF₃CO₂H, HBF₄, CF₃CO₂H/NaB[C₆H₃(CF₃)₂]₄, and picric acid C₆H₂(NO₂)₃OH afforded salts 2•X (X = CF₃CO₂, BF₄, B[C₆H₃(CF₃)₂]₄), and (2,3,4,5-tetram ethylruthenocenyl)methyl picrate [CpRu(C₅Me₄CH₂)-η⁶][(C₆H₂(NO₂)₃O] (2•C₆H₂(NO₂)₃O). Structure of the latter was characterized by single crystal X-ray diffraction.     

AB initio molecular orbital studies of CF3O2H,CF3O2F and CF2(OF)2

Ab initio calculations employing an extended 4-31G basis set have been applied to the highly fluorinated molecules, CF₃O₂H, CF₃O₂F and CF₂(OF)₂. Partial geometry optimizations have also been carried out on these molecules allowing a comparison between theory and the recently completed gas-phase electron diffraction results. The O-O bond distance in CF₃O₂ H is found to be longer (by 0.02 Å) than the corresponding bond in CF₃O₂F while the CO bond is found to be shorter (by 0.02 Å) in CF₃O₂H. The OF bond in CF₃O₂F is found to be longer (by 0.03–0.04 Å) than the corresponding bond in CF₃OF or F₂O. Torsional barriers have been computed for CF₃O₂H and CF₃O₂F with the aid of Fourier analysis of the potential curves. CF₃O₂H is found to have a torsional potential about the peroxide bond rather similar to that found for H₂O₂ while in CF₃O₂F the cis and trans barriers are predicted to be much larger (14.6 and 8.4 kcal mol^?1, respectively). The threefold barrier to rotation of the CF₃ group in CF₃O₂F is predicted to be 4.4 kcal mol^?1. Various conformations of CF₂(OF)₂ have also been studied with conformations consistent with the operation of the gauche-effect being most stable. Bond separation energies and molecular properties have also been computed for these molecules.     

The reaction of boron trihalides with CF3Sn(CH3)3 in the presence of trimethylamine

The reaction of CF₃Sn(CH₃)₃ with BCl₃ and BBr₃ in the presence of trimethylamine has been investigated. The volatile adducts CF₂XBF₂·N(CH₃)₃ (X = F, Cl and Br) have been isolated from the complex reaction mixture while the anions BF^?₄, CF₂XBF^?₃, CF₃BF₂CF₂X^? and (CF₂X)₂BF^?₂ have been identified in the residue. [(CH₃)₃NH][CF₂ClBF₃] has been isolated. The formation of the CF₂XB derivatives is likely to occur via CF₂ insertion, which is promoted by the presence of N(CH₃)₃. NMR, IR, Raman and mass spectra of the novel fluoromethyl borane derivatives are reported.     

The syntheses and mass spectra of P[CCCF3]3, As[CCCF3]3, and Sb[CCCF3]3

The syntheses of P[CCCF₃]₃, As[CC CF₃]₃, and Sb[CCCF₃]₃ are reported. The compounds are colorless and volatile, with melting points of ?20° to ?25°, 23–24°, and 55–56°C, respectively. The mass spectra show the molecular ion of each compound. The rearrangement ion [F₃CCCCCCF₂]⁺] gives the strongest peak in each spectrum.     

A Novel Dimeric Polyoxotungstate Decorated by 3d-4f atoms: K4LaH[As2W20CuO67 (H2O)3]Cl2· 22.5H2O

A novel dimeric polyoxotungstate K₄LaH[As₂W₂₀CuO₆₇(H₂O)₃ ]Cl₂·22.5H₂O has been synthesized and characterized by IR, element analysis TG and cyclic voltammogram. The anion K₄LaH[As₂W₂₀CuO₆₇(H₂O) ₃]Cl₂·22.5H₂O can be characterized as two {As^IIIW₉O₃₃}⁹⁻ moieties linked via a {Cu(OH)}, a {W(H₂O)} and a {WO(H₂O)} group which total coordination numbers are respectively 5, 5, 6. An additional lanthanide atom connects the dimeric cluster via a W-O-La bond. The X-ray single crystal diffraction shows that it is in the triclinic system, space group P-1, with a = 12.287(6) ?, b = 20.197(1) ?,c=21.483(1)?,α = 62.584(8)°,β = 74.659(8)°,γ = 75.273(9)°,V = 4509(4)?³, Z = 2. To our known, the polyoxotungstate is the novel sandwich-type polyoxoanion, which is decorated by transition-metal and lanthanide atoms at the same time.     

Ein fünffach koordinierter ionischer zirkonium(IV)-komplex mit der (π-C5H5)2ZrIV-Baueinheit: [(π-C5H5)2Zr(H2O)3]2+(CF3SO3−)2·THF

The ionic complex [(π-C₅H₅)₂Zr(H₂O)₃]²⁺(CF₃SO₃^?)₂·THF, which corresponds to the 18-electron rule, is formed in the reaction of (π-C₅H₅)₂Zr(CF₃SO₃)₂(THF) with H₂O in tetrahydrofuran. It crystallizes in the hexagonal space group P6₃ with Z = 6 and unit cell dimensions at ? 100°C of a 21.945(5) and c 8.711(3) Å. The geometry of the (π-C₅H₅)₂Zr moiety (length of the vectors between Zr and the C₅ ring centroids: 2.210 and 2.193 Å; angle between these vectors: 129.0°; angle between the C₅ ring normals: 128.3°) agrees with that of neutral, four-coordinate (π-C₅H₅)₂ZrX₂ compounds. The three H₂O ligands lie in the plane that bisects the angle between the C₅ ring planes. The ZrO distances are 2.239(7), 2.195(7), and 2.261(7) Å. The CF₃SO₃^? anions and the THF molecule of crystallization are packed around the complex cation in such a way that their oxygen atoms point towards the H₂O ligands. The CF₃ sides of the anion, on the other hand, are clustered together so as to produce hydrophobic domains in the crystal structure.     

Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]•0.5bipy•3H2O配合物的合成、晶体结构及荧光性质

在水-乙醇混合体系中, 以2-羰基丙酸水杨酰腙(C₁₀H₁₀N₂O₄)、2,2-联吡啶(C₁₀H₈N₂, 简写bipy)与Eu(NO₃)₃•4H₂O反应, 首次培养出黄色单晶[Eu(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H₂O)₃]•0.5bipy•3H₂O. 该晶体属三斜晶系, 空间群为P-1, 晶胞参数a＝0.93392(16) nm, b＝1.3100(2) nm, c＝1.3895(2) nm, α＝97.205(3)°, β＝105.411(2)°, γ＝106.364(2)°, V＝15.35(2) nm³, Z＝2, μ＝2.118 mm^－1, D_c＝1.686 Mg/m³, F(000)＝786, R＝0.0116, wR＝0.0507, GOF＝0.995. 晶体测试结果表明, 该单晶结构为铕的9配位配合物, 两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C＝N中的氮与Eu^3＋配位, 形成两个共边的稳定五元环, 另三个配位原子则分别来自三个水分子中的氧原子, 该配合物在空间呈扭曲的单帽四方反棱柱, 而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子, 这些游离分子与配位分子之间存在大量分子内和分子间氢键, 整个分子在空间呈三维网状结构. 发光性能测试表明该配合物具有很好的荧光性质.     

Synthese,Kristallstruktur und magnetisches Verhalten von Gd(CF3CF2COO)3(H2O)3

Synthesis, Crystal Structure and Magnetic Behaviour of Gd(CF₃CF₂COO)₃(H₂O)₃ Single crystals of Gd(CF₃CF₂COO)₃(H₂O)₃ have been obtained by reaction of Gd₂O₃ with an aqueous solution of CF₃CF₂COOH. The compound crystallizes triclinically in the space group (No. 2; Z = 2; a = 928.5(1) pm, b = 1037.1(1) pm, c = 1147.3(2) pm, α = 90.44(2)°, β = 108.56(1)°, γ = 106.49(1)°). In the crystal structure the gadolinium ions are bridged by carboxylate groups to dimers and are coordinated eightfold by oxygen atoms. The magnetic behaviour was investigated in the temperature range of 1.77 to 300 K. The magnetic data indicate weak antiferromagnetic interactions within the dimeric unit (J_ex = ?0.0057 cm^?1).     

Laser photolysis of C2H2 and CF3C2H at 193 nm: Production of C2(d3Πg and CH(A2Δ) and their quenching by Xe

The 193 nm laser photodissociation of CH₂H₂ and CF₃C₂H has been studied. With the laser beam focused, C₂(d³Π_g) and CH(A²Δ) radicals were formed by multiphoton processes in both C₂H₂ and CF₃C₂H; however, the one-photon process forming C₂H is still predominant in CF₃C₂H photolysis. The production of C₂(d³Π_g) and CH(A²Δ) emissions is prompt,and the emission intensities show similar (less than quadratic) dependence on laser power whether the radicals are produced from C₂H₂ or CF₃C₂H. In addition, the vibrational distribution of the Swan system is nearly the same in CF₃C₂H as in C₂H₂. The results indicate that the overall photolytic processes are similar in two molecules. Both the C₂(d³Π_g) and CH(A²Δ) emissions are quenched by Xe with rate constants of 4.8×10^?11 and 1.8×10^?11 cm³ molecule^?1 s^?1, respectively.     

Synthesis and structure of the heterotrinuclear chromium-palladium clusters (RC5H4CrCl)2-(μ3S)(μ-SCMe3)2Pd(PPh3) with ferromagnetic exchange interactions over the CrSCr system

Reactions of (RC₅H₄)₂Cr₂(SCMe₃)₂S(I, R = H; II, R = Me) with (PPh₃)₂PdCl₂ in benzene at 20°C gives trinuclear complexes (RC₅H₄)₂Cr₂Cl₂(μ₃-S)(μ-SCMe₃)₂Pd(PPh₃)(III, R = H; IV, R = Me). The structure of IV as a monobenzene solvate is established by an X-ray analysis (black-green triclinic crystals space group P$\text{1}$ with a = 11.403(4), b = 14.933(5), c = 14.131(5) Å, α = 99.13(3), β = 112.72(3), γ = 95.65(3)°, V = 2201.6 Å, Z = 2; IV·C₆H₆). The structure was solved by direct methods and refined in an anisotropic approximation to R = 0.046, R_w = 0.058 for 7643 reflections with I ? 2σ(I). In the molecule of IV metal atoms are separated by non-bonding distances (Cr … Cr 4.079(I), Cr … Pd 3.230(I) and 3.380(I) Å) but linked by the bridging tridentate sulphur atom (CrS 2.339(2) and 2.329(2), PdS 2.327(2) Å), and two SCMe₃ groups between Pd and Cr (CrS 2.396(2) and 2.403(2), PdS 2.350(2) and 2.381(2) Å, Cr?Pd 85.14(6) and 89.92(6)°). The Cl atoms are transferred from Pd to Cr atoms (CrCl 2.308(2) Å) and being terminally coordinated are in trans-positions to each other (as well as η-CH₃C₅H₄ rings) with respect to the Cr₂Pd plane. Cr atoms in III and IV exhibit ferromagnetic exchange interactions over the Cr?Cr system (+2J = 28 and 11 cm^?1, respectively).     

Collisional quenching of K* (4p2p) and K* (5p2p by H2O,CF4, and CH4

Rate constants are reported for collisional quenching of K^* (4p^2p and K^* (5p^2p) by H₂O, CF₄ and CH₄. The K^* (4p^2p or K^*(5p^2p) is produced by photodissociation of K1 vapor at 2450 Å or 1925 Å, respectively. As for Na^* (3p^2p, H₂O, CF₄, and CH₄ are very inefficient at quenching K^* (4p^2p); however, they are very efficient at quenching K^* (5p^2p).     

1-Allyl derivatives: Synthesis and crystal structures for [(NH2C5H4N(C3H5))2Cu3Cl3(NO3)2] and [C9H7N(C3H5)Cu(NO3)2]

1-Allyl-4-aminopyridinium chloride reacts with Cu(NO₃)₂ · 3H₂O in an ethanolic solution under the conditions of ac electrochemical synthesis at copper electrodes to form crystals of compound [(NH₂C₅H₄N(C₃H₅))₂Cu₃Cl₃(NO₃)₂] (I). The crystals of compound I are monoclinic: space group P2₁/c, Z = 4, a = 25.770(7), b = 7.230(4), c = 12.505(5) ?, β = 92.58(3)°, V = 2328(2) ?³. The direct interaction of 1-allylquinolinium nitrate with Cu(NO₃)₂ · 3H₂O in a methanolic solution in the presence of metallic copper yields crystals of compound [C₉H₇N(C₃H₅)Cu(NO₃)₂] (II). The crystals of compound II are triclinic: space group P , a = 6.756(3), b = 8.391(4), c = 12.489(5) ?, α = 77.18(3)°, β = 89.48(4)°, γ = 73.32(3)°, V = 662.0(5) ?³. The structure of compound I is built of infinite linear anions: polymeric fragments {(NH₂C₅H₄N(C₃H₅))₂Cu₃Cl₃(NO₃)₂} _n . Each of two copper atoms (Cu(1) and Cu(2)) π-coordinates the C=C bonds of the allyl groups of the 1-allyl-4-aminopyridinium cations, the oxygen atom of the nitrate ions, and two chlorine atoms. The third copper atom Cu(3) is linearly linked with two chlorine atoms. Particular polymeric fragments are additionally joined by the N-H…O, C-H…O, C-H…Cl hydrogen bonds. The crystal structure of compound II is built-up of the isolated L₂Cu₂(NO₃)₄ fragments (L is the 1-allylquinolinium cation). The metal atom is localized in the trigonal pyramidal coordination environment of three oxygen atoms of the nitrate ions and of the C=C bond of the allyl group of the cation. The particular L₂Cu₂(NO₃)₄ fragments are additionally joined by the C-H…O hydrogen bonds. Original Russian Text ? A.V. Pavlyuk, T. Lis, M.G. Mys’kiv, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No. 6, pp. 458–462.     

Deactivation of I(52P1/2) by CF3I,CH3I,C2H5I,and CH4

The technique of laser photolysis of alkyl and perfluoroalkyl iodides at 266 nm followed by time-resolved detection of the 1.3-μm emission from I^*(²P_1/2) has been used to measure the rate constants for deactivation of I^* by CH₃I, C₂H₅I, CF₃I, and CH₄. The recommended values are (2.76± 0.22) × 10^?13, (2.85 ± 0.40) × 10^?13, (3.5 ± 0.5) × 10^?17, and (7.52 ± 0.12) × 10^?14, respectively, in units of cm³ molecule^?1 S^?1.     

Mercury-photosensitized luminescence of NH3 and ND3 at low pressure

The mercury-photosensitized luminescence of ammonia has been investigated at low pressures. The emission spectrum with [ND₃] = 0.005 torr consisted of two peaks at 305 and 340 nm. The 305 nm band was assigned to the complex in the higher electronic state which correlates with Hg(³P₁). At limiting zero pressure, the complex formation in the higher state predominates, while the 340 nm band is in the ascendant at higher pressure. Results obtained in the presence of third-bodies, M = C₂H₆, CH₄, CF₄, N₂, and Ne have been also reported.     

Crystal and molecular structure of tricyclopentadienyltetrahydrofuranuranium(III), (η5-C5H5)3U·OC4H8

Tricyclopentadienyltetrahydrofuranuranium(III), (η⁵-C₅H₅)₃U·OC₄H₈, crystallizes in the centrosymmetric monoclinic space group P2₁/n with a 8.248(3), b 24.322(17), c 8.357(4) Å, β 101.29(5)°, V 1644.0 ų and ρ(calc) 2.04 g cm^?1 for Z = 4 and mol.wt. 595.0. Diffraction data (Mo-K_α, 2θ(max) 45°) were collected on an Enraf-Nonius CAD4 diffractometer and the structure was refined to R_w(F) 4.7% for those 1530 reflections having I > 2σ(I). The molecule consists of a distorted tetrahedral arrangement of THF and (η⁵-C₅H₅) ligands with CpUCp angles in the range 110.4–122.4° and CpUO angles between 90.2 and 106.0°. Individual uranium-carbon distances range from 2.76(2) to 2.82(2) Å and average 2.79[1] Å. The uranium-oxygen distance of 2.551(10) Å suggests a 10-coordinate U³⁺ radius of 1.20 Å in this class of compounds.     

Perfluoralkyljod-verbindungen: Darstellungen und eigenschaften von CF3JO,CF3JOF2 und CF3JO2

Perfluoroalkyl iodine compounds: preparations and properties of CF₃IO, CF₃IOF₂, and CF₃IO₂. The trifluoromethyl iodine compounds CF₃IO, CF₃IOF₂, and CF₃IO₂ are formed from the reactions of CF₃I, CF₃IF₂ or CF₃IF₄ with ozone or silicon dioxide respectively. Their preparartions, properties, ¹⁹F-nmr spectra, and ir spectra are described.