Synthesis and Characterization by (19)F and (125)Te NMR and Raman Spectroscopy of cis-ReO(2)(OTeF(5))(3) and cis-ReO(2)(OTeF(5))(4)(-), and X-ray Crystal Structure of [N(CH(3))(4)(+)][cis-ReO(2)(OTeF(5))(4)(-)

The pentafluorooxotellurate compound ReO(2)(OTeF(5))(3) has been synthesized from the reaction of ReO(2)F(3) with B(OTeF(5))(3) and structurally characterized in solution by (19)F and (125)Te NMR spectroscopy and in the solid state by Raman spectroscopy. The NMR and vibrational spectroscopic findings are consistent with a trigonal bipyramidal arrangement in which the oxygen atoms and an OTeF(5) group occupy the equatorial plane. The (19)F and (125)Te NMR spectra show that the axial and equatorial OTeF(5) groups of ReO(2)(OTeF(5))(3) are fluxional and are consistent with intramolecular exchange by means of a pseudorotation. The Lewis acid behavior of ReO(2)(OTeF(5))(3) is demonstrated by reaction with OTeF(5)(-). The resulting cis-ReO(2)(OTeF(5))(4)(-) anion was characterized as the tetramethylammonium salt in solution by (19)F and (125)Te NMR spectroscopy and in the solid state by Raman spectroscopy and X-ray crystallography. The compound crystallizes in the triclinic system, space group P&onemacr;, with a = 13.175(7) ?, b = 13.811(5) ?, c = 15.38(1) ?, alpha = 72.36(5)(o), beta = 68.17(5)(o), gamma = 84.05(4)(o), V = 2476(2) ?(3), D(calc) = 3.345 g cm(-)(3), Z = 4, R = 0.0547. The coordination sphere about Re(VII) in cis-ReO(2)(OTeF(5))(4)(-) is a pseudooctahedron in which the Re-O double bond oxygens are cis to one another.     

Mixed-metal uranium(VI) iodates: hydrothermal syntheses,structures, and reactivity of Rb[UO(2)(CrO(4))(IO(3))(H(2)O)], A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K,Rb, Cs), and K(2)[UO(2)(MoO(4))(IO(3))(2)

The reactions of the molecular transition metal iodates A[CrO(3)(IO(3))] (A = K, Rb, Cs) with UO(3) under mild hydrothermal conditions provide access to four new, one-dimensional, uranyl chromatoiodates, Rb[UO(2)(CrO(4))(IO(3))(H(2)O)] (1) and A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K (2), Rb (3), Cs (4)). Under basic conditions, MoO(3), UO(3), and KIO(4) can be reacted to form K(2)[UO(2)(MoO(4))(IO(3))(2)] (5), which is isostructural with 2 and 3. The structure of 1 consists of one-dimensional[UO(2)(CrO(4))(IO(3))(H(2)O)](-) ribbons that contain uranyl moieties bound by bridging chromate and iodate anions as well as a terminal water molecule to create [UO(7)] pentagonal bipyramidal environments around the U(VI) centers. These ribbons are separated from one another by Rb(+) cations. When the iodate content is increased in the hydrothermal reactions, the terminal water molecule is replaced by a monodentate iodate anion to yield 2-4. These ribbons can be further modified by replacing tetrahedral chromate anions with MoO(4)(2)(-) anions to yield isostructural, one-dimensional [UO(2)(MoO(4))(IO(3))(2)](2)(-) ribbons. Crystallographic data: 1, triclinic, space group P(-)1, a = 7.3133(5) A, b = 8.0561(6) A, c = 8.4870(6) A, alpha = 88.740(1) degrees, beta = 87.075(1) degrees, gamma = 71.672(1) degrees, Z = 2; 2, monoclinic, space group P2(1)/c, a = 11.1337(5) A, b = 7.2884(4) A, c = 15.5661(7) A, beta = 107.977(1) degrees, Z = 4; 3, monoclinic, space group P2(1)/c, a = 11.3463(6) A, b = 7.3263(4) A, c = 15.9332(8) A, beta = 108.173(1) degrees, Z = 4; 4, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4; 5, monoclinic, space group P2(1)/c, a = 11.3717(6) A, b = 7.2903(4) A, c = 15.7122(8) A, beta = 108.167(1) degrees, Z = 4.     

Cation ordering in natural and synthetic (Cu(1-x)Zn(x))(2)CO(3)(OH)(2) and (Cu(1-x)Zn(x))(5)(CO(3))(2)(OH)(6)

In the present paper we report combined experimental and theoretical studies of the UV-vis-NIR spectra of the mineral compounds malachite, rosasite, and aurichalcite and of the precursor compounds for Cu/ZnO catalysts. For the copper species in the minerals the crystal field splitting and the vibronic coupling constants are estimated using the exchange charge model of the crystal field accounting for the exchange and covalence effects. On this basis the transitions responsible for the formation of the optical bands arising from the copper centers in minerals are determined and the profiles of the absorption bands corresponding to these centers are calculated. The profiles of the absorption bands calculated as a sum of bands of their respective Cu species are in quite good agreement with the experimental data. In agreement with crystal chemical considerations, the Zn ions were found to be preferentially located on the more regular, i.e., less distorted, octahedral sites in zincian malachite and rosasite, suggesting a high degree of metal ordering in these phases. This concept also applies for the mineral aurichalcite, but not for synthetic aurichalcite, which seems to exhibit a lower degree of metal ordering. The catalyst precursor was found to be a mixture of zincian malachite and a minor amount of aurichalcite. The best fit of the optical spectrum is obtained assuming a mixture of contributions from malachite (0% Zn) and rosasite (38% Zn of [Zn + Cu]), which is probably due to the intermediate Zn content of the precursor (30%).     

Synthesis and characterization of six new quaternary actinide thiophosphate compounds: Cs(8)U(5)(P(3)S(10))(2)(PS(4))(6)(,) K(10)Th(3)(P(2)S(7))(4)(PS(4))(2), and A(5)An(PS(4))(3), (A = K, Rb, Cs; An = U, Th)

Six new actinide metal thiophosphates have been synthesized by the reactive flux method and characterized by single-crystal X-ray diffraction: Cs(8)U(5)(P(3)S(10))(2)(PS(4))(6) (I), K(10)Th(3)(P(2)S(7))(4)(PS(4))(2) (II), K(5)U(PS(4))(3) (III), K(5)Th(PS(4))(3) (IV), Rb(5)Th(PS(4))(3) (V), and Cs(5)Th(PS(4))(3) (VI). Compound I crystallizes in the monoclinic space group P2(1)/c with a = 33.2897(1) A, b = 14.9295(1) A, c = 17.3528(2) A, beta = 115.478(1) degrees, Z = 8. Compound II crystallizes in the monoclinic space group C2/c with a = 32.8085(6) A, b = 9.0482(2) A, c = 27.2972(3) A, beta = 125.720(1) degrees, Z = 8. Compound III crystallizes in the monoclinic space group P2(1)/c with a = 14.6132(1) A, b = 17.0884(2) A, c = 9.7082(2) A, beta = 108.63(1) degrees, Z = 4. Compound IV crystallizes in the monoclinic space group P2(1)/n with a = 9.7436(1) A, b = 11.3894(2) A, c = 20.0163(3) A, beta = 90.041(1) degrees, Z = 4, as a pseudo-merohedrally twinned cell. Compound V crystallizes in the monoclinic space group P2(1)/c with a = 13.197(4) A, b = 9.997(4) A, c = 18.189(7) A, beta = 100.77(1) degrees, Z = 4. Compound VI crystallizes in the monoclinic space group P2(1)/c with a = 13.5624(1) A, b = 10.3007(1) A, c = 18.6738(1) A, beta = 100.670(1) degrees, Z = 4. Optical band-gap measurements by diffuse reflectance show that compounds I and III contain tetravalent uranium as part of an extended electronic system. Thorium-containing compounds are large-gap materials. Raman spectroscopy on single crystals displays the vibrational characteristics expected for [PS(4)](3)(-), [P(2)S(7)](4-), and the new [P(3)S(10)](5)(-) building blocks. This new thiophosphate building block has not been observed except in the structure of the uranium-containing compound Cs(8)U(5)(P(3)S(10))(2)(PS(4))(6).     

Syntheses and Properties of New Layered Alkali-Metal/Ammonium Vanadium(V) Methylphosphonates: M(VO(2))(3)(PO(3)CH(3))(2) (M = NH(4), K, Rb, Tl). Single-Crystal Structures of K(VO(2))(3)(PO(3)CH(3))(2) and NH(4)(VO(2))(3)(PO(3)CH(3))(2)

The hydrothermal syntheses of a family of new alkali-metal/ammonium vanadium(V) methylphosphonates, M(VO(2))(3)(PO(3)CH(3))(2) (M = K, NH(4), Rb, Tl), are described. The crystal structures of K(VO(2))(3)(PO(3)CH(3))(2) and NH(4)(VO(2))(3)(PO(3)CH(3))(2) have been determined from single-crystal X-ray data. Crystal data: K(VO(2))(3)(PO(3)CH(3))(2), M(r) = 475.93, trigonal, R32 (No. 155), a = 7.139(3) ?, c = 19.109(5) ?, Z = 3; NH(4)(VO(2))(3)(PO(3)CH(3))(2), M(r) = 454.87, trigonal, R32 (No. 155), a = 7.150(3) ?, c = 19.459(5) ?, Z = 3. These isostructural, noncentrosymmetric phases are built up from hexagonal tungsten oxide (HTO) like sheets of vertex-sharing VO(6) octahedra, capped on both sides of the V/O sheets by PCH(3) entities (as [PO(3)CH(3)](2-) methylphosphonate groups). In both phases, the vanadium octahedra display a distinctive two short + two intermediate + two long V-O bond distance distribution within the VO(6) unit. Interlayer potassium or ammonium cations provide charge balance for the anionic (VO(2))(3)(PO(3)CH(3))(2) sheets. Powder X-ray, TGA, IR, and Raman data for these phases are reported and discussed. The structures of K(VO(2))(3)(PO(3)CH(3))(2) and NH(4)(VO(2))(3)(PO(3)CH(3))(2) are compared and contrasted with related layered phases based on the HTO motif.     

Bildung von NH4[Hg3(NH)2](NO3)3 und Umwandlung in [Hg2N](NO3)

Formation of NH₄[Hg₃(NH)₂](NO₃)₃ and Transformation to [Hg₂N](NO₃) NH₄[Hg₃(NH)₂](NO₃)₃ ( 1 ) and [Hg₂N](NO₃) ( 2 ) are obtained from conc. aqueous ammonia solutions of Hg(NO₃)₂ at ambient temperature and under hydrothermal conditions at 180 °C, respectively, as colourless and dark yellow to light brown single crystals. The crystal structures {NH₄[Hg₃(NH)₂](NO₃)₃: cubic, P4₁32, a = 1030.4(2) pm, Z = 4, R_all = 0.028; [Hg₂N](NO₃): tetra gonal, P4₃2₁2, a = 1540.4(1), c = 909.8(1) pm, Z = 4, R_all = 0.054} have been determined from single crystal data. Both exhibit network type structures in which [HNHg₃] and [NHg₄] tetrahedra of the partial structures of 1 and 2 are connected via three and four vertices, respectively. 1 transforms at about 270 °C in a straightforward reaction to 2 whereby the decomposition products of NH₄NO₃ are set free. 2 decomposes at about 380 °C forming yellow HgO. Most certainly, 1 is identical with a mineral previously analyzed as “Hg(NH₂)(NO₃)” with the same Hg:N:O ratio.     

Small gas-phase dianions of Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-)

We have searched for new species of small oxygen-containing gas-phase dianions produced in a secondary ion mass spectrometer by Cs+ ion bombardment of solid samples with simultaneous exposure of their surfaces to O2 gas. The targets were a pure zinc metal foil, a copper-contaminated zinc-based coin, two silicon-germanium samples (Si(1-x)Ge(x)(with x= 6.5% or 27%)) and a piece of titanium metal. The novel dianions Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-) have been observed at half-integer m/z values in the negative ion mass spectra. The heptamer dianions Zn3O(4)(2-) and Ti2O(5)(2-) have been unambiguously identified by their isotopic abundances. Their flight times through the mass spectrometer are approximately 20 micros and approximately 17 micros, respectively. The geometrical structures of the two heptamer dianions Ti2O(5)(2-), and Zn3O(4)(2-) are investigated using ab initio methods, and the identified isomers are compared to those of the novel Ge2O(5)(2-) and the known Si2O(5)(2-) and Be3O(4)(2-) dianions.     

Thiophosphate phase diagrams developed in conjunction with the synthesis of the new compounds KLaP(2)S(6), K(2)La(P(2)S(6))(1/2)(PS(4)), K(3)La(PS(4))(2), K(4)La(0.67)(PS(4))(2), K(9-)(x)La(1+x/3)(Ps(4))(4) (x = 0.5), K(4)Eu(PS(4))(2), and KEuPS(4)

An alkali-metal sulfur reactive flux has been used to synthesize a series of quaternary rare-earth metal compounds. These include KLaP(2)S(6) (I), K(2)La(P(2)S(6))(1/2)(PS(4)) (II), K(3)La(PS(4))(2) (III), K(4)La(0.67)(PS(4))(2) (IV), K(9-x)La(1+x/3)(PS(4))(4) (x = 0.5) (V), K(4)Eu(PS(4))(2) (VI), and KEuPS(4) (VII). Compound I crystallizes in the monoclinic space group P2(1)/c with the cell parameters a = 11.963(12) A, b = 7.525(10) A, c = 11.389(14) A, beta = 109.88(4) degrees, and Z = 4. Compound II crystallizes in the monoclinic space group P2(1)/n with a = 9.066(6) A, b = 6.793(3) A, c = 20.112(7) A, beta = 97.54(3) degrees, and Z = 4. Compound III crystallizes in the monoclinic space group P2(1)/c with a= 9.141(2) A, b = 17.056(4) A, c = 9.470(2) A, beta = 90.29(2) degrees, and Z = 4. Compound IV crystallizes in the orthorhombic space group Ibam with a = 18.202(2) A, b = 8.7596(7) A, c = 9.7699(8) A, and Z = 4. Compound V crystallizes in the orthorhombic space group Ccca with a = 17.529(9) A, b = 36.43(3) A, c = 9.782(4) A, and Z = 8. Compound VI crystallizes in the orthorhombic space group Ibam with a = 18.29(5) A, b = 8.81(2) A, c= 9.741(10) A, and Z = 4. Compound VII crystallizes in the orthorhombic space group Pnma with a = 16.782(2) A, b = 6.6141(6) A, c = 6.5142(6) A, and Z = 4. The sulfur compounds are in most cases isostructural to their selenium counterparts. By controlling experimental conditions, these structures can be placed in quasi-quaternary phase diagrams, which show the reaction conditions necessary to obtain a particular thiophosphate anionic unit in the crystalline product. These structures have been characterized by Raman and IR spectroscopy and UV-vis diffuse reflectance optical band gap analysis.     

Expanding the remarkable structural diversity of uranyl tellurites: hydrothermal preparation and structures of K[UO(2)Te(2)O(5)(OH)], Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O,beta-Tl(2)[UO(2)(TeO(3))(2)], and Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2)

The reactions of UO(2)(C(2)H(3)O(2))(2).2H(2)O with K(2)TeO(3).H(2)O, Na(2)TeO(3) and TlCl, or Na(2)TeO(3) and Sr(OH)(2).8H(2)O under mild hydrothermal conditions yield K[UO(2)Te(2)O(5)(OH)] (1), Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O (2) and beta-Tl(2)[UO(2)(TeO(3))(2)] (3), or Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2) (4), respectively. The structure of 1 consists of tetragonal bipyramidal U(VI) centers that are bound by terminal oxo groups and tellurite anions. These UO(6) units span between one-dimensional chains of corner-sharing, square pyramidal TeO(4) polyhedra to create two-dimensional layers. Alternating corner-shared oxygen atoms in the tellurium oxide chains are protonated to create short/long bonding patterns. The one-dimensional chains of corner-sharing TeO(4) units found in 1 are also present in 2. However, in 2 there are two distinct chains present, one where alternating corner-shared oxygen atoms are protonated, and one where the chains are unprotonated. The uranyl moieties in 2 are bound by five oxygen atoms from the tellurite chains to create seven-coordinate pentagonal bipyramidal U(VI). The structures of 3 and 4 both contain one-dimensional [UO(2)(TeO(3))(2)](2-) chains constructed from tetragonal bipyramidal U(VI) centers that are bridged by tellurite anions. The chains differ between 3 and 4 in that all of the pyramidal tellurite anions in 3 have the same orientation, whereas the tellurite anions in 4 have opposite orientations on each side of the chain. In 4, there are also additional isolated TeO(3)(2-) anions present. Crystallographic data: 1, orthorhombic, space group Cmcm, a = 7.9993(5) A, b = 8.7416(6) A, c = 11.4413(8) A, Z = 4; 2, orthorhombic, space group Pbam, a = 10.0623(8) A, b = 23.024(2) A, c = 7.9389(6) A, Z = 4; 3, monoclinic, space group P2(1)/n, a = 5.4766(4) A, b = 8.2348(6) A, c = 20.849(3) A, beta = 92.329(1) degrees, Z = 4; 4, monoclinic, space group C2/c, a = 20.546(1) A, b = 5.6571(3) A, c = 13.0979(8) A, beta = 94.416(1) degrees, Z = 4.     

Triangular oxalate clusters [W(3)(mu(3)-S)(mu(2)-S(2))(3)(C(2)O(4))(3)](2)(-) as building blocks for coordination polymers and nanosized complexes

The reaction of aqueous [W3S7(C2O4)3](2-) with Ln(3+) and Th(4+) in a 1:1 molar ratio leads to oxalate-bridged heteropolynuclear molecular complexes and coordination polymers. La(3+) and Ce(3+) give a layered structure with big (about 1.8 nm) honeycomb pores which are filled with water molecules and lanthanide ions, in {[Ln(H2O)6]3[W3S7(C2O4)3]4}Br x xH2O (Ia and Ib). The smaller Pr(3+), Nd(3+), Sm(3+), Eu(3+), and Gd(3+) ions give discrete nanomolecules [(W3S7(C2O4)3Ln(H2O)5)2(mu-C2O4)] (with a separation of about 3.2 nm between the most distant parts of the molecule), which are further united into zigzag chains by specific S2...Br- contacts to achieve the overall stoichiometry K[(W3S7(C2O4)3Ln(H2O)5)2(mu-C2O4)]Br.xH2O (IIa-IId). Th(4+) gives K2[(W3S7(C2O4)3)4Th2(OH)2(H2O)10] x 14.33H2O (III) with a nanosized discrete anion (with a separation of about 2.7 nm between the most distant parts of the molecule), in which two thorium atoms are bound via two hydroxide groups into the Th2(OH)2(6+) unit, and each Th is further coordinated by five water molecules and two monodentate [W3S7(C2O4)](2-) cluster ligands. All compounds were characterized by X-ray structure analysis and IR spectroscopy. Magnetic susceptibility measurements in the temperature range of 2-300 K show weak antiferromagnetic interactions between two lanthanides atoms for compounds IIa, IIb, and IId. The thermal decomposition of Ia, Ib, and IIb was studied by thermogravimetry.     

Selenophosphate phase diagrams developed in conjunction with the synthesis of the new compounds K(2)La(P(2)Se(6))(1/2)(PSe(4)), K(3)La(PSe(4))(2), K(4)La(0.67)(PSe(4))(2), K(9-x)La(1+x/3)(PSe(4))(4) (x = 0.5), and KEuPSe(4)

Five new rare-earth metal polyselenophosphates have been synthesized by the reactive flux method and characterized by single-crystal X-ray diffraction: K(2)La(P(2)Se(6))(1/2)(PSe(4)) (I), K(3)La(PSe(4))(2) (II), K(4)La(0.67)(PSe(4))(2) (III), K(9-x)()La(1+)(x/3)(PSe(4))(4) (x = 0.5) (IV), and KEuPSe(4) (V). Compound I crystallizes in the monoclinic space group P2(1)/n with a = 9.4269(1) A, b = 7.2054(1) A, c = 21.0276(5) A, beta = 97.484(1) degrees, and Z = 4. Compound II crystallizes in the monoclinic space group P2(1)/c with a = 9.5782(2) A, b = 17.6623(4) A, c = 9.9869(3) A, beta = 90.120(1) degrees, and Z = 4. Compound III crystallizes in the orthorhombic space group Ibam with a = 19.0962(2) A, b = 9.1408(1) A, c = 10.2588(2) A, and Z = 4. Compound IV crystallizes in the orthorhombic space group Ccca with a = 18.2133(1) A, b = 38.0914(4) A, c = 10.2665(1) A, and Z = 8. Compound V crystallizes in the orthorhombic space group Pnma with a = 17.5156(11) A, b = 7.0126(5) A, c = 6.9015(4) A, and Z = 4. Optical band gap measurements show that compound V has an optical band gap of 1.88 eV. Solid-state Raman spectroscopy of compounds II-V shows the four normal vibrations expected for the (PSe(4))(3-) unit. The observation of compounds I-V in several reactions has allowed the creation of a quasi-quaternary phase diagram for potassium rare-earth-metal polyselenophosphates. This phase diagram can qualitatively be separated into three regions on the basis of the oxidation state of phosphorus in the crystalline products observed and takes the next step in designing solid-state compounds.     

Halogenomercurate: Darstellung und Strukturen von [Cu(en)2][Hg2Cl6], [Cu(en)2][Hg2Br6] und [Cu(en)2][HgBr4]

Halomercurates: Syntheses and Crystal Structures of [Cu(en)₂][Hg₂Cl₆], [Cu(en)₂][Hg₂Br₆], and [Cu(en)₂][HgBr₄] Crystals of [Cu(en)₂][Hg₂Cl₆] ( 1 ) have been obtained by layering a solution of Hg(NO₃)₂ and NaCl with a solution of [Cu(en)₂]SO₄. An analogous procedure, using NaBr instead of NaCl, gave crystals of [Cu(en)₂][HgBr₄] ( 3 ). Crystals of [Cu(en)₂][Hg₂Br₆] ( 2 ) were obtained by gel crystallization using the same starting materials as for 3 . The complexes show very low solubility. The dinuclear anions of 1 consist of two nearly planar HgCl₃ units related by a center of symmetry. In 2 infinite anionic chains are present, made up of parallel HgBr₃ units. These units are packed in such a way as to produce a trigonal bipyramidal configuration around the Hg atoms. 3 contains mononuclear deformed tetrahedral [HgBr₄]^2– anions. In all three complexes the packing of the ions is such that halogen atoms of halomercurate anions complete a tetragonal bipyramidal coordination at Cu. The resulting Cu–Halogen distances are 2.924 Å for 1 , 3.036 Å for 2 and 3.085 and 3.119 Å for 3 . 1 : Space group P 1, Z = 1, lattice constants at 20 °C: a = 7.000(2), b = 7.526(2), c = 8.239(2) Å; α = 88.39(2), β = 86.06(2), γ = 86.10(3)°; R₁ = 0.040. 2 : Space group P2₁/c, Z = 2, lattice constants at –50 °C: a = 7.185(1), b = 16.338(2), c = 7.814(1) Å; β = 94.88(2)°; R₁ = 0.033. 3 : Space group P2₁/n, Z = 4, lattice constants at 20 °C: a = 8.055(3), b = 13.101(3), c = 13.814(3) Å; β = 91.24(3)°; R₁ = 0.092.     

Metal(II) hexafluorophosphates(V) (M = Sr, Pb) containing XeF(2)-coordinated metal ions [M(XeF(2))(3)](PF(6))(2), [Pb(3)(XeF(2))(11)](PF(6))(6), and [Sr(3)(XeF(2))(10)](PF(6))(6)

From the system MF(2)/PF(5)/XeF(2)/anhydrous hydrogen fluoride (aHF), four compounds [Sr(XeF(2))(3)](PF(6))(2), [Pb(XeF(2))(3)](PF(6))(2), [Sr(3)(XeF(2))(10)](PF(6))(6), and [Pb(3)(XeF(2))(11)](PF(6))(6) were isolated and characterized by Raman spectroscopy and X-ray single-crystal diffraction. The [M(XeF(2))(3)](PF(6))(2) (M = Sr, Pb) compounds are isostructural with the previously reported [Sr(XeF(2))(3)](AsF(6))(2). The structure of [Sr(3)(XeF(2))(10)](PF(6))(6) (space group C2/c; a = 11.778(6) Angstrom, b = 12.497(6) Angstrom, c = 34.60(2) Angstrom, beta = 95.574(4) degrees, V = 5069(4) Angstrom(3), Z = 4) contains two crystallographically independent metal centers with a coordination number of 10 and rather unusual coordination spheres in the shape of tetracapped trigonal prisms. The bridging XeF(2) molecules and one bridging PF(6)- anion, which connect the metal centers, form complicated 3D structures. The structure of [Pb(3)(XeF(2))(11)](PF(6))(6) (space group C2/m; a = 13.01(3) Angstrom, b = 11.437(4) Angstrom, c = 18.487(7) Angstrom, beta = 104.374(9) degrees, V = 2665(6) Angstrom(3), Z = 2) consists of a 3D network of the general formula {[Pb(3)(XeF(2))(10)](PF(6))(6)}n and a noncoordinated XeF(2) molecule fixed in the crystal structure only by weak electrostatic interactions. This structure also contains two crystallographically independent Pb atoms. One of them possesses a unique homoleptic environment built up by eight F atoms from eight XeF(2) molecules in the shape of a cube, whereas the second Pb atom with a coordination number of 9 adopts the shape of a tricapped trigonal prism common for lead compounds. [Pb(3)(XeF(2))(11)](PF(6))(6) and [Sr(3)(XeF(2))(10)](PF(6))(6) are formed when an excess of XeF(2) is used during the process of the crystallization of [M(XeF(2))(3)](PF(6))(2) from their aHF solutions.     

Toward rational control of metal stoichiometry in heterobimetallic coordination complexes: synthesis and characterization of Pb(Hsal)2(Cu(salen*))2, [Pb(NO3)(Cu(salen*))2](NO3), Pb(OAc)2(Cu(salen*)), and [Pb(OAc)(Ni(salen*))2](OAc)

The ability of the transition metal complex M(salen)* (M = Ni, Cu) to form Lewis acid-base adducts with lead(II) salts has been explored. The new complexes Pb(Hsal)(2)(Cu(salen*))(2) (1), [Pb(NO(3))(Cu(salen*))(2)](NO(3)) (2), Pb(OAc)(2)(Cu(salen*)) (3), and [Pb(OAc)(Ni(salen*)(2)](OAc) (4) (Hsal = O(2)CC(6)H(4)-2-OH, salen* = bis(3-methoxy)salicylideneimine) have been synthesized and characterized spectroscopically and by single-crystal X-ray diffraction. The coordination environment of the lead in the heterobimetallic complex is sensitive both to the initial lead salt and to the transition metal salen* complex that is employed in the synthesis. As a result, we have been able to access both 2:1 and 1:1 adducts by varying either the lead salt or the transition metal in the heterobimetallic coordination complex. In all cases, the salen* complex is associated with the lead center via dative interactions of the phenolic oxygen atoms. The relationship between the coordination requirements of the lead and the chemical nature of the anion is examined. In compound 1, the Pb(2+) ion is chelated by two Cu(salen*) moieties, and both salicylate ligands remain attached to the lead center and bridge to the Cu(2+) ions. The two Cu(salen*) groups are roughly parallel and opposed to each other as required by crystallographic inversion symmetry at lead. In contrast, the two Cu(salen*) groups present in 2 and 4 attached to the lead ion show considerable overlap. Furthermore, only one nitrate ion in 2 and one acetate ion in 4 remain bonded to the lead center. Compound 3 is unique in that only one Cu(salen*) group can bind to lead. Here, both acetate ligands remain attached, although one is chelating bidentate and the other is monodentate.     

Ni(II), Pd(II), Cu(II) And Zn(II) complexes with N-(2-Pyridyl)Carbonylaniline (L), Syntheses and X-Ray Crystal structures of [Cu(L)2(H2O)2](No3)2, [Cu(L)2(H2O)2](Clo4)2 and [Zn(L)2(H2O)2](Clo4)2

Reaction of the N-(2-pyridyl)carbonylaniline ligand (L) with Cu(NO₃)₂, Cu(ClO₄)₂, Zn(ClO₄)₂, Ni(NO₃)₂ and PdCl₂ gives complexes with stoichiometry [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, [Zn(L)₂(H₂O)₂] (ClO₄)_2, [Ni(L)₂(H₂O)Cl](NO₃) and PdLCl₂. The new complexes were characterized by elemental analyses and infrared spectra. The crystal structures of [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, and [Zn(L)₂(H₂O)₂](ClO₄)₂ were determined by X-ray crystallography. The cation complexes [M(L)₂(H₂O)₂] contain copper(II) and zinc(II) with distorted octahedral geometry with two N-(2-pyridyl)carbonylaniline (L) ligands occupying the equatorial sites. The hexa-coordinated metal atoms are bonded to two pyridinic nitrogens, two carbonyl oxygens and two water molecules occupying the axial sites. Both the coordinated water molecules and uncoordinated amide NH groups of the N-(2-pyridyl)carbonylaniline (L) ligands are involved in hydrogen bonding, resulting in infinite hydrogen-bonded chains running in one and two-dimensions.     

New class of ruthenium sulfide clusters: Ru(4)S(6)(PPh(3))(4), Ru(5)S(6)(PPh(3))(5), and Ru(6)S(8)(PPh(3))(6)

Reaction of RuCl(2)(PPh(3))(3) with S(2)(-) sources yields a family of phosphine-containing Ru-S clusters which have been characterized crystallographically and by MALDI-MS. Ru(4)S(6)(PPh(3))(4) (Ru-Ru(av) = 2.94 A) has idealized T(d)() symmetry whereas Ru(6)S(8)(PPh(3))(6) (Ru-Ru(av) = 2.82 A) adopts the idealized O(h)() symmetry characteristic of Chevrel clusters. Ru(5)S(6)(PPh(3))(5) is formally derived by the addition of Ru(PPh(3)) to one face of Ru(4)S(6)(PPh(3))(4). In terms of its M-S connectivity, the Ru(5)S(6) cluster resembles a fragment of the FeMo cluster in nitrogenase.     

Synthesis and characterization of [Cu(mb2en)2]ClO4 and [Cu(mb2en)(PPh3)2]BPh4: crystal structure of [Cu(mb2en)2]ClO4

The ligand, N,N′-bis-(4-methoxy-benzylidene)-ethane-1,2-diamine (mb₂en), and its corresponding copper(I) complexes, [Cu(mb₂en)₂]ClO₄ (1), and [Cu(mb₂en)(PPh₃)₂]BPh₄ (2), have been synthesized and characterized by CHN analyses, ¹H and ¹³C-NMR, IR, and UV-Vis spectroscopies. The crystal and molecular structure of [Cu(mb₂en)₂]ClO₄ (1), were determined by X-ray crystallography from a single-crystal. The coordination polyhedron about copper(I) is best described as a distorted tetrahedron. Quasi-irreversible redox behavior was observed for 1 and 2 (E _1/2?=?0.55 and 0.95?V, respectively).     

Copper and Bismuth Complexes Containing Dipyridyl gem-Diolato Ligands: Bi(III)(2)[(2-Py)(2)CO(OH)](2)(O(2)CCF(3))(4)(THF)(2), Cu(II)[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), and Cu(II)(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), a Ferromagnetically Coupled Tetranuclear Copper(II) Chain

The reactions of the singly deprotonated di-2-pyridylmethanediol ligand (dpmdH(-)) with copper(II) and bismuth(III) have been investigated. A new dinuclear bismuth(III) complex Bi(2)(dpmdH)(2)(O(2)CCF(3))(4)(THF)(2), 1, has been obtained by the reaction of BiPh(3) with di-2-pyridyl ketone in the presence of HO(2)CCF(3) in tetrahydrofuran (THF). The reaction of Cu(OCH(3))(2) with di-2-pyridyl ketone, H(2)O, and acetic acid in a 1:2:2:2 ratio yielded a mononuclear complex Cu[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), 2, while the reaction of Cu(OAC)(2)(H(2)O) with di-2-pyridyl ketone and acetic acid in a 2:1:1 ratio yielded a tetranuclear complex Cu(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), 3. The structures of these complexes were determined by single-crystal X-ray diffraction analyses. Three different bonding modes of the dpmdH(-) ligand were observed in compounds 1-3. In 2, the dpmdH(-) ligand functions as a tridentate chelate to the copper center and forms a hydrogen bond between the OH group and the noncoordinating HO(2)CCH(3) molecule. In 1 and 3, the dpmdH(-) ligand functions as a bridging ligand to two metal centers through the oxygen atom. The two pyridyl groups of the dpmdH(-) ligand are bound to one bismuth(III) center in 1, while in 3 they are bound two copper(II) centers, respectively. Compound 3 has an unusual one dimensional hydrogen bonded extended structure. The intramolecular magnetic interaction in 3 has been found to be dominated by ferromagnetism. Crystal data: 1, C(38)H(34)N(4)O(14)F(12)Bi(2), triclinic P&onemacr;, a = 11.764(3) ?, b = 11.949(3) ?, c = 9.737(1) ?, alpha =101.36(2) degrees, beta = 105.64(2) degrees, gamma = 63.79(2) degrees, Z = 1; 2, C(26)H(26)N(4)O(8)Cu/CH(2)Cl(2), monoclinic C2/c, a = 25.51(3) ?, b = 7.861(7) ?, c = 16.24(2) ?, beta = 113.08(9) degrees, Z = 4; 3, C(34)H(40)N(4)O(18)Cu(4)/CH(2)Cl(2), triclinic P&onemacr;, a = 10.494(2) ?, b = 13.885(2) ?, c = 7.900(4) ?, alpha =106.52(2) degrees, beta = 90.85(3) degrees, gamma = 94.12(1) degrees, Z = 1.