Synthesis and characterisation of HRuRh3(CO)12. Crystal structures of HRuRh3(CO)12, HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2

A new ruthenium-rhodium mixed-metal cluster HRuRh₃(CO)₁₂ and its derivatives HRuRh₃(CO)₁₀(PPh₃)₂ and HRuCo₃(CO)₁₀(PPh₃)₂ have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh₃(CO)₁₂: monoclinic, space group P2₁/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh₃(CO)₁₀(PPh₃)₂·C₆H₁₄: triclinic, space group P$\text{1}$, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo₃(CO)₁₀(PPh₃)₂·CH₂Cl₂: triclinic, space group P$\text{1}$, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)₄^? and (Ru(CO)₃Cl₂)₂ tetrahydrofuran followed by acid treatment yields HRuRh₃(CO)₁₂ in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh₃(CO)₁₀(PPh₃)₂, which is closely related to HRuCo₃(CO)₁₀(PPh₃)₂ and HFeCo₃(CO)₁₀(PPh₃)₂. The phosphines are axially coordinated.     

Non-centrosymmetric Ba3Ti3O6(BO3)2

The compound previously reported as Ba₂Ti₂B₂O₉ has been reformulated as Ba₃Ti₃B₂O₁₂, or Ba₃Ti₃O₆(BO₃)₂, a new barium titanium oxoborate. Small single crystals have been recovered from a melt with a composition of BaTiO₃:BaTiB₂O₆ (molar ratio) cooled between 1100°C and 850°C. The crystal structure has been determined by X-ray diffraction: hexagonal system, non-centrosymmetric space group, a=8.7377(11) Å, c=3.9147(8) Å, Z=1, wR(F²)=0.039 for 504 unique reflections. Ba₃Ti₃O₆(BO₃)₂ is isostructural with K₃Ta₃O₆(BO₃)₂. Preliminary measurements of nonlinear optical properties on microcrystalline samples show that the second harmonic generation efficiency of Ba₃Ti₃O₆(BO₃)₂ is equal to 95% of that of LiNbO₃.     

Hydrothermal Syntheses, Structures, and Properties of Two New Potassium Vanadium Phosphates: K3(VO) (V2O3) (PO4)2(HPO4) and K3 (VO) (HV2O3) (PO4)2(HPO4)

Two new potassium vanadium phosphates have been prepared and their structures have been determined from analysis of single crystal X-ray data. The two compounds, K₃(VO)(V₂O₃) (PO₄)₂(HPO₄) and K₃(VO)(HV₂O₃)(PO₄)₂(HPO₄), are isostructural, except for the incorporation of an extra hydrogen atom into the nearly identical frameworks. The structures consist of a three-dimensional network of [VO]_n chains connected through phosphate groups to a [V₂O₃] moiety. Magnetic susceptibility experiments indicate that in the case of the di-hydrogen compound, there are no significant magnetic interactions between the three independent vanadium (IV) centers. Crystal data: for K₃(VO)(V₂O₃)(PO₄)₂ (HPO₄), M_r = 620.02, orthorhombic space group Pnma (No. 62), a = 7.023(4) Å, b = 13.309(7) Å, c = 14.294(7) Å, V = 1336(2) ų, Z = 4, R = 5.02%, and R_w = 5.24% for 1238 observed reflections [I > 3σ(I)]; for K₃(VO)(HV₂O₃)(PO₄)₂(HPO₄), M_r = 621.04, orthorhombic space group Pnma (No. 62), a = 6.975(3) Å, b = 13.559(7) Å, c = 14.130(7) Å, V = 1336(1) ų, Z = 4, R = 6.02%, and R_w = 6.34% for 1465 observed reflections [I > 3σ(I)].     

Structure of two new borates YCa3(AlO)3(BO3)4 and YCa3(GaO)3(BO3)4

By replacing Mn in YCa₃(MnO)₃(BO₃)₄ with trivalent Al and Ga, two new borates with the compositions of YCa₃(MO)₃(BO₃)₄ (M=Al, Ga) were prepared by solid-state reaction. Structure refinements from X-ray powder diffraction data revealed that both of them are isostructural to gaudefroyite with a hexagonal space group P6₃/m. Cell parameters of a=10.38775(13)Å, c=5.69198(10)Å for the Al-containing compound and a=10.5167(3)Å, c=5.8146(2)Å for the Ga analog were obtained from the refinements. The structure is constituted of AlO₆ or GaO₆ octahedral chains interconnected by BO₃ groups in the ab plane to form a Kagomé-type lattice, leaving trigonal and apatite-like tunnels. It is found that most rare-earth and Cr, Mn ions can be substituted into the Y³⁺ and M³⁺ sites, respectively, and the preference of rare-earth ions to locate in the trigonal tunnel is correlated to the sizes of the M³⁺ ions.     

Syntheses, crystal structures, and properties of three new metal selenites Na2Co2(SeO3)3, Na2Co1.67Ni0.33(SeO3)3, and Na2Ni2(SeO3)3

Three new sodium cobalt (nickel) selenite compounds, namely, Na₂Co₂(SeO₃)₃, Na₂Co_1.67Ni_0.33(SeO₃)₃, and Na₂Ni₂(SeO₃)₃ have been hydro-/solvothermally synthesized in the mixed solvents of acetonitrile and water. Single-crystal X-ray diffraction analyses reveal that these isostructural compounds belong to the orthorhombic Cmcm space group and their structures feature three-dimensional open frameworks constructed by the two-dimensional layers of [MSeO₃] pillared by the [SeO₃]²⁻ groups. The two different types of Na⁺ ions reside in the intersecting two-dimensional channels parallel to the a- and c-axes, respectively. Their thermal properties have been investigated via TGA-DSC. The magnetic measurements indicate the existence of the antiferromagnetic interactions in these compounds.     

Luminescence properties of efficient X-ray phosphors of YBa3B9O18, LuBa3(BO3)3, α-YBa3(BO3)3 and LuBO3

The samples of YBa₃B₉O₁₈, LuBa₃(BO₃)₃, α-YBa₃(BO₃)₃ and LuBO₃ powders have been synthesized by the solid-state reaction methods at high temperature and their X-ray excited luminescent properties were investigated. All the studied materials show a broad emission band in the wavelength range of 300-550 nm with the peak centers at about 385 nm for YBa₃B₉O₁₈ and LuBa₃(BO₃)₃, 415 nm for α-YBa₃(BO₃)₃ and 360 nm for LuBO₃ powders, respectively. Even though those compounds have the different atomic structures, they have the common structural feature of each yttrium or lutetium ion bonded to six separate BO₃ groups, i.e., octahedral RE(BO₃)₆ (RE=Lu or Y) moiety. This octahedral RE(BO₃)₆(RE=Lu or Y) moiety seems to be an important structural element for efficient X-ray excited luminescence of those compounds, as are the edge-sharing octahedral TaO₆ chains for tantalate emission.     

Synthesis and molecular structures of heptafluoroisopropylated fullerenes: C60(i-C3F7)8, C60(i-C3F7)6, and C60(CF3)2(i-C3F7)2

One isomer of C₆₀(i-C₃F₇)₈, three isomers of C₆₀(i-C₃F₇)₆, and the first mixed perfluoroalkylated fullerene, C₆₀(CF₃)₂(i-C₃F₇)₂, have been isolated by HPLC from a mixture prepared by reaction of C₆₀ with heptafluoroisopropyl iodide in a glass ampoule at 260-290 °C. The molecular structures of the four new compounds have been determined by means of X-ray single crystal diffraction partially also by use of synchrotron radiation. Theoretical calculations at the DFT level of theory have been employed to rationalize the energetics of isomers and of C₆₀-R_f binding.     

The molecular structures of H2Os3(CO)10, H(SC2H5)Os3(CO)10 and (OCH3)2Os3(CO)10

X-ray crystallographic analyses of H₂Os₃(CO)₁₀, H(SC₂H₅)Os₃(CO)₁₀ and (OCH₃)₂Os₃(CO)₁₀ are reported. Although hydrogen atom positions have not been located, the essential isostructural nature of the three commplexes establishes the hydride ligands as bridging two metal atoms, separated by 2.670 Å, with a formal bond order of two; the bridging hydrido- and thiolato-ligands span an osmium---osmium bond of length 2.863 Å and formal bond order one; the two μ-methoxy ligands bridge two metal atoms separated by 3.078 Å which, by simple 18 electron rule counting, has a metal---metal bond order of zero. Some general comments are made on the structures of polynuclear transition metal carbonyls.     

Vibrational spectra of the peroxotantalates (NH4)3[Ta(O2)4], K3[Ta(O2)4], Rb3[Ta(O2)4] and Cs3[Ta(O2)4] and the crystal structure of Rb3[Ta(O2)4]

The compounds (NH₄)₃[Ta(O₂)₄], K₃[Ta(O₂)₄], Rb₃[Ta(O₂)₄] and Cs₃[Ta(O₂)₄] have been prepared and investigated by X-ray powder methods as well as Raman- and IR-spectroscopy. In the case of Rb₃[Ta(O₂)₄] the structure has been solved from single crystal data. It is shown that all these compounds are isotypic and crystallize in the K₃[Cr(O₂)₄] type (SG , No. 121). The infrared- and Raman spectra (recorded on powdered samples) are discussed with respect to the internal vibrations of the peroxo-group and the dodecahedral [Ta(O₂)₄]³⁻ ion. Symmetry coordinates for the [Ta(O₂)₄]³⁻ ion are given from which the vibrational modes of the O-O stretching vibrations of the O₂²⁻ groups, the Ta-O stretching vibrations and the Ta-O bending vibrations are deduced.     

Thermal decomposition of organo-bielemental vanadium compounds Cp2V(ER3) (ER3 - GeEt3, SnEt3, CH2SiMe3 SeGeEt3)

The thermal decompositon of a number of organo-bielemental vanadium compounds with the general formula Cp₂V(ER₃) (ER₃ - GeEt₃, SnEt₃, CH₂SiMe₃, SeGeEt₃) has been investigated in solids and in solution. The main decomposition products of Cp₂V(SnEt₃) are vanadocene and hexaethyldistannane. Et₃GeH, Et₃GeCp, Cp₂V and CpV(C₅H₄GeEt₃) are formed from Cp₂V (GeET₃) decomposition. Isolated CpV(C₅H₄GeEt₃) is characterized by IR and mass spectra. The decomposition of Cp₂V(CH₂SiMe₃) is accompanied by Me₄Si, Cp₂V and CpV-(C₅H₄CH₂SiMe₃) formation, the latter is identified from the mass spectrum. Triethylgermane, vanadocene, and a diselenide of vanadium are isolated on decomposition of Cp₂V(SeGeEt₃). Based upon the experimental data, mechanisms for the decompositon are proposed.     

New thallium iodates—Synthesis, characterization, and calculations of Tl(IO3)3 and Tl4(IO3)6, [Tl3Tl(IO3)6]

Two new thallium iodates have been synthesized, Tl(IO₃)₃ and Tl₄(IO₃)₆ [Tl⁺₃Tl³⁺(IO₃)₆], and characterized by single-crystal X-ray diffraction. Both materials were synthesized as phase-pure compounds through hydrothermal techniques using Tl₂CO₃ and HIO₃ as reagents. The materials crystallize in space groups R-3 (Tl(IO₃)₃) and P-1 (Tl₄(IO₃)₆). Although lone-pairs are observed for both I⁵⁺ and Tl⁺, electronic structure calculations indicate the lone-pair on I⁵⁺ is stereo-active, whereas the lone-pair on Tl⁺ is inert.     

Synthesis and molecular structure of [Au3Ru4(μ3-H)(CO)12(PPh3)3]

The title compound can be prepared in good yield by heating either [Ru₄(μ-H)₄(CO)₁₂] or [Au₂Ru₄(μ₃-H)₂(CO)₁₂(PPh₃)₂] with [AuMe(PPh₃)] in toluene. The related compound [Au₃Ru₄(μ₃-H)(μ-dppm)(CO)₁₂(PPh₃)] has also been prepared. Both trigoldtetraruthenium clusters undergo dynamic behaviour in solution, involving intramolecular rearrangement of the metal core, as revealed by variable temperature NMR studies. The crystal structure of [Au₃Ru₄(μ₃-H)(CO)₁₂(PPh₃)₃] has been established by an X-ray diffraction study. The metal atom core comprises a trigonal bipyramidal AuRu₄ unit with two AuRu₂ faces capped by gold atoms.     

Vaporization of DyI3(s) and thermochemistry of the homocomplexes (DyI3)2(g) and (DyI3)3(g)

The vaporization of DyI₃(s) was investigated in the temperature range between 833 and 1053 K by the use of Knudsen effusion mass spectrometry. The ions DyI₂⁺, DyI₃⁺, Dy₂I₄⁺, Dy₂I₅⁺, Dy₃I₇⁺, and Dy₃I₈⁺ were detected in the mass spectrum of the equilibrium vapor. The gaseous species DyI₃, (DyI₃)₂, and (DyI₃)₃ were identified and their partial pressures determined. Enthalpies and entropies of sublimation resulted according to the second- and third-law methods. The following sublimation enthalpies at 298 K were determined for the gaseous species given in brackets: 274.8±8.2 kJ mol⁻¹ [DyI₃], 356.0±11.3 kJ mol⁻¹ [(DyI₃)₂], and 436.6±14.6 kJ mol⁻¹ [(DyI₃)₃]. The enthalpy changes of the dissociation reactions (DyI₃)₂=2 DyI₃ and (DyI₃)₃=3 DyI₃ were obtained as Δ_dH°(298)=193.3±5.6 and 390.3±13.0 kJ mol⁻¹, respectively.     

Pd(PBu 3 t ) Adducts of Os3(CO)12. Synthesis and Structures of Pd2Os3(CO)12(PBu 3 t )2 and Pd3Os3(CO)12 (PBu 3 t )3

Two new compounds Pd₂Os₃(CO)₁₂ , 13 and Pd₃Os₃(CO)₁₂ , 14 have been obtained from the reaction of with Os₃(CO)₁₂ at room temperature. The products were formed by the addition of two and three groups to the Os–Os bonds of Os₃(CO)₁₂. Compounds 13 and 14 interconvert between themselves by intermolecular exchange of the groups in solution. Compounds 13 and 14 have been characterized by single crystal X-ray diffraction analyses.Dedicated to Professor Brian F. G. Johnson on the occasion of his retirement – 2005.     

Synthesis and structural characterization of two cobalt phosphites: 1-D (H3NC6H4NH3)Co(HPO3)2 and 2-D (NH4)2Co2(HPo3)3

Two new cobalt phosphites, (H₃NC₆H₄NH₃)Co(HPO₃)₂ (1) and (NH₄)₂Co₂(HPO₃)₃ (2), have been synthesized and characterized by single-crystal X-ray diffraction. All the cobalt atoms of 1 are in tetrahedral CoO₄ coordination. The structure of 1 comprises twisted square chains of four-rings, which contain alternating vertex-shared CoO₄ tetrahedra and HPO₃ groups. These chains are interlinked with trans-1,4-diaminocyclohexane cations by hydrogen bonds. The 2-D structure of 2 comprises anionic complex sheets with ammonium cations present between them. An anionic complex sheet contains three-deck phosphite units, which are interconnected by Co₂O₉ to form complex layers. Magnetic susceptibility measurements of 1 and 2 showed that they have a weak antiferromagnetic interaction.     

Syntheses, structures, and properties of Ag4(Mo2O5)(SeO4)2(SeO3) and Ag2(MoO3)3SeO3

Ag₄(Mo₂O₅)(SeO₄)₂(SeO₃) has been synthesized by reacting AgNO₃, MoO₃, and selenic acid under mild hydrothermal conditions. The structure of this compound consists of cis-MoO₂²⁺ molybdenyl units that are bridged to neighboring molybdenyl moieties by selenate anions and by a bridging oxo anion. These dimeric units are joined by selenite anions to yield zigzag one-dimensional chains that extended down the c-axis. Individual chains are polar with the C₂ distortion of the Mo(VI) octahedra aligning on one side of each chain. However, the overall structure is centrosymmetric because neighboring chains have opposite alignment of the C₂ distortion. Upon heating Ag₄(Mo₂O₅)(SeO₄)₂(SeO₃) looses SeO₂ in two distinct steps to yield Ag₂MoO₄. Crystallographic data: (193 K; MoKα, λ=0.71073 Å): orthorhombic, space group Pbcm, a=5.6557(3), b=15.8904(7), c=15.7938(7) Å, V=1419.41(12), Z=4, R(F)=2.72% for 121 parameters with 1829 reflections with I>2σ(I). Ag₂(MoO₃)₃SeO₃ was synthesized by reacting AgNO₃ with MoO₃, SeO₂, and HF under hydrothermal conditions. The structure of Ag₂(MoO₃)₃SeO₃ consists of three crystallographically unique Mo(VI) centers that are in 2+2+2 coordination environments with two long, two intermediate, and two short bonds. These MoO₆ units are connected to form a molybdenyl ribbon that extends along the c-axis. These ribbons are further connected together through tridentate selenite anions to form two-dimensional layers in the [bc] plane. Crystallographic data: (193 K; MoKα, λ=0.71073 Å): monoclinic, space group P2₁/n, a=7.7034(5), b=11.1485(8), c=12.7500(9) Å, β=105.018(1) V=1002.7(2), Z=4, R(F)=3.45% for 164 parameters with 2454 reflections with I>2σ(I). Ag₂(MoO₃)₃SeO₃ decomposes to Ag₂Mo₃O₁₀ on heating above 550 °C.     

Conductivities of the Ternary Systems Y(NO3)3+La(NO3)3+H2O, La(NO3)3+Ce(NO3)3+H2O, La(NO3)3+Nd(NO3)3+H2O and Their Binary Subsystems at Different Temperatures

Electrical conductivities were measured for the ternary systems Y(NO₃)₃+La(NO₃)₃+H₂O, La(NO₃)₃+Ce(NO₃)₃+H₂O, La(NO₃)₃+Nd(NO₃)₃+H₂O, and their binary subsystems Y(NO₃)₃+H₂O, La(NO₃)₃+H₂O, Ce(NO₃)₃+H₂O, and Nd(NO₃)₃+H₂O at (293.15, 298.15 and 308.15) K. The measured conductivities were used to test the generalized Young’s rule and the semi-ideal solution theory. The comparison results show that the generalized Young’s rule and the semi-ideal solution theory can yield good predictions for the conductivities of the ternary electrolyte solutions, implying that the conductivities of aqueous solutions of (1:3 + 1:3) electrolyte mixtures can be well predicted from those of their constituent binary solutions by the simple equations.     

Ni-P-Zn3(PO4)2(ZnSnO3、ZnSiO3)纳米复合化学镀层性质和组成的研究

研究了温度、时间、浓度等对Ａ３钢片上Ｎi-P-Zn3(PO4)2、Ni-P-ZnSnO3和Ｎi-P-ZiSiO3纳米复合合化学镀层外貌的影响,用扫描电子显微镜（ＳＥＭ）观察外貌、称重法测定厚度;通过１０％ＮaCl溶液、１％Ｈ２Ｓ气体加速腐蚀试验,１０％ＣuSO4溶液点滴试验等多种手段测定其耐腐蚀性能,用Ｘ－射线光电子谱（ＸＰＳ）及俄歇电子能谱（ＳＥＳ）测定其价态组成,结果表明：在最佳施镀条件下,可得光亮、致密、耐腐蚀性强于Ａ３钢、磷化膜及Ｎi-P镀层的纳米复合化学镀层,镀层的原子百分组成约为（％）：Ｎi-P-Zn3(PO4)2:Ni70.00,P12.47,Zn3(PO4)213.93,C3.6;Ni-P-ZnSnO3;Ni77.56,P10.00,ZnSnO39.84,C2.6;Ni-P-NiSiO3,Ni83.00,P10.96,ZnSi5.15,C0.89.     

Ba3 (VO4)2-K2 Ba(MoO4)2 and Pb3 (VO4)2-K2 Pb(MoO4)2 systems

Phase equilibria in the Ba₃(VO₄)₂-K₂Ba(MoO₄)₂ and Pb3(VO₄)₂-K₂Pb(MoO₄)₂ systems have been investigated. In the first system, a continuous series of substitutional solid solutions with the palmierite structure is formed, and in the second one, the polymorphic transition in lead orthovanadate at 100°C restricts the extent of the palmierite-type solid solution to 10–100 mol % K₂Pb(MoO₄)₂. Original Russian Text ? V.D. Zhuravlev, Yu.A. Velikodnyi, A.S. Vinogradova-Zhabrova, A.P. Tyutyunnik, V.G. Zubkov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 10, pp. 1746–1748.     

Reactions of Ru3(CO)12 with Ene-yne and Alkoxy-silyl Functionalized Compounds. The Crystal Structure of (μ-H)Ru3(CO)9[μ3-η2-HC=N(CH2)3Si(OEt)3]

Ru₃(CO)₁₂ has been reacted with the compounds hex-1-en-3-yne [EtC≡CCH=CH₂], 2-methyl-hex-1-en-3-yne [EtC≡CC(=CH₂)CH₃] and with 3(ethoxy-silyl)propyl isocyanate [(EtO)₃Si(CH₂)₃NCO] and the compound tb [(EtO)₃Si(CH₂)₃NHC(=O)OCH₂C≡CCH₂OC(=O)NH(CH₂)₃Si(OEt)₃] in hydrocarbon solution. Some reactions in CH₃OH/KOH solution (followed by acidification) have also been performed. The main products of the reactions with ene-ynes are the clusters Ru₃(CO)₆(μ-CO)₂L₂ (L = C₆H₈, C₇H₁₀) and their demolition products, the “ferrole” Ru₂(CO)₆L₂ complexes. One of the isomers of Ru₃(CO)₆(μ-CO)₂L₂, and Ru₂(CO)₆L₂ (L = C₇H₁₀) have been reacted with vinyl-triethoxysilane [(EtO)₃SiCH=CH₂]: these reactions did not afford complexes containing new carbon–carbon bonds or triethoxy-silyl groups. Only polymerization of vinyl-triethoxysilane occurred. The reactions of Ru₃(CO)₁₂ with triethoxysilyl-propyl-isocyanate and tb (in the presence of Me₃NO) lead to the same products, that is the isomeric complexes (μ-H)Ru₃(CO)₉[C=N(H)(CH₂)₃Si(OEt)₃] with a “perpendicular” ligand (complex 3, as proposed on the basis of spectroscopic results) and (μ-H)Ru₃(CO)₉[HC=N(CH₂)₃Si(OEt)₃] with a “parallel” ligand (complex 4, as confirmed by a X-ray analysis). The reaction pathways leading to these products are discussed. Complex 4 has been reacted with tetraethyl orthosilicate and the resulting material has been characterized. These reactions are part of a study on the synthesis of inorganic-organometallic materials through sol–gel techniques. This paper is dedicated to Prof. Gunther Schmid in the occasion of his 70th birthday.