Novel rhenium oxocomplexes of indazole-3-carboxylic acid – Synthesis,X-ray studies,spectroscopic characterization and DFT calculations

Three novel rhenium oxocomplexes incorporating indazole-3-carboxylate ligand: cis-[ReOCl₂(Ind-3-COO)(PPh₃)]·OPPh₃ (1a), cis-[ReOCl₂(Ind-3-COO)(PPh₃)] (1b) and cis-[ReOBr₂(Ind-3-COO)(PPh₃)]·OPPh₃ (2) have been synthesized and characterised spectroscopically and structurally (by single-crystal X-ray diffraction). The 1a and 2 are isostructural in solid state. The electronic spectrum of 1a was investigated at the TDDFT level employing B3LYP functional in combination with LANL2DZ. Additional information about binding in the complex 1a was obtained by NBO analysis.     

对苯二甲酸邻菲咯啉铽钇配合物的红外光谱及荧光光谱研究

以对苯二甲酸和邻菲咯啉为配体，不同摩尔比铽钇离子为中心体，合成了系列配合物，研究了红外光谱及荧光光谱。结果表明，对苯二甲酸中羧基氧和邻菲咯啉中的氮原子原与稀土离子配位，以邻菲咯啉（Phe)和对苯二甲酸根（L）为配体的配合物（TbxY1-x)2(Phen)2L3中，不发光的Y^3 对发光的Tb^3＋的荧光强强度有明显的增强作用，交联配体对苯二甲比非交联体传递所吸收的能量更加有效。     

树形大分子/金属配合物及其纳米复合材料的制备与性能研究进展

树形大分子是具有确定代数和末端基的蓬勃发展的新型合成高分子。大量具有不同的中心核、支链和末端基团的树形大分子已经被合成和应用于不同的领域,其功能化和应用是目前树形大分子研究领域的热点。本文综述了树形大分子/金属配合物及其纳米复合材料的制备与性能的研究进展,重点介绍了树形大分子/金属配合物材料和树形大分子/金属纳米复合材料的制备与性能研究的最新进展。     

Synthesis, characterization and reactivity of tetracyclopentadienylniobium(IV), a precursor to organometallic derivatives of niobium(IV)

In toluene as medium, tetra(cyclopentadienyl)niobium(IV), NbCp₄, has been prepared in satisfactory yields from the reaction of NaCp with: (a) Nb₂C1₁₀, (b) NbCl₄(THF)₂, or (c) NbCp₂Cl₂. Tetracyclopentadienylniobium(IV) has been characterized by X-ray diffraction. Crystal data: C₂₀H₂₀Nb, M=353.29 g mol⁻¹, hexagonal, space group P6₅ (no. 170), a=b=9.396(2), c=31.23(3) Å, V=2388(2) ų, Z=6, d_calc=1.48 g cm⁻³, λ(Cu–K)=1.54184 Å, T=291 K, μ=62.04 cm⁻¹, F(000)=1686. Two of the four cyclopentadienyl ligands are bonded to niobium in a pentahapto fashion, the other two being monohapto. NbCp₄ undergoes cyclopentadiene elimination in the presence of species containing active protons such as Ph₃SiOH or strong acids, the products being tris- or biscyclopentadienyl compounds depending on the molar ratio of the reagents.     

Synthesis and Structural Studies of Some β-Diketone Phenylhydrazones and their Complexes with Co(II), Ni(II), and Cu(II)

Summary.  New β-diketone phenylhydrazones prepared by condensation of substituted 3-arylidene-2,4-pentanediones with phenylhydrazine, have been characterized by their elemental analyses, IR, ¹H NMR, and mass spectra. Some complexes of these Schiff bases with Co(II), Ni(II), and Cu(II) ions have been synthesized; in addition to the above methods, their structures were studied by magnetic susceptibility and thermogravimetry measurements. Received January 26, 2000. Accepted (revised) April 14, 2000     

配合物EuxM1-x(TTA)3(H2O)2(M=La,Gd)光致发光特性

合成了一系列组成为EuxM1－x(TTA)3(H2O)2(M=La,Gd)的固体配合物,利用红外光谱和荧光光谱研究了配合物结构和发光性质随Eu3＋浓度的变化规律.红外光谱的结果表明,配合物的成份为Eu(TTA)3(H2O)2和M(TTA)3(H2O)2,没有新化合物生成.而荧光光谱的结果显示配合物的发光强度与Eu3＋浓度不成线性关系,其中不发光的M(TTA)3组分对发光有增益作用.对其可能的发光机制进行了探讨.     

Na4ReN3, das erste Alkalimetall‐Nitridorhenat(V)

Na₄ReN₃, the First Alkali Metal Nitridorhenate(V) Rhenium powder reacts in a mixture with NaNH₂ in autoclaves at 773 K to orange colored crystals embedded in a matrix of sodium metal. After extracting the sodium metal with liquid ammonia single crystals were seperated. The structure was solved by X‐ray single crystal methods and for the evaluation of the correct space group by optical SHG experiments: spacegroup Cc (No. 9), Z = 4, a = 10.903(2) Å, b = 6.022(1) Å, c = 8.944(2) Å, β = 115.57(3)°. The structure contains trigonal pyramidal anions ReN₃^4–, which are embedded in three‐dimensionally linked, fourfold capped cubes of 12 Na.     

Synthesis and Crystal Structure of (PCl4)[Re2Cl9]

The reaction between PCl₃ and ReCl₅ yielded at 200 °C the ionic tetrachlorophosphonium dirhenium nonachloride, (PCl₄)[Re₂Cl₉]. Single crystal X-ray diffraction analysis revealed a monoclinic unit cell: a = 8.616(3) Å, b = 10.449(4) Å, c = 9.397(3) Å, β = 99.72(3)°, V = 833.9(5) ų, Z = 2, sp. gr. P2₁/m, wR₂ = 0.1083 and R₁ = 0.0527. The ionic compound is built from tetrahedra PCl₄⁺ and face-sharing bioctahedra Re₂Cl₉^–. The Re–Re distance, 2.724 Å, indicates the presence of direct Re-Re interaction.     

Über das Tri(phosphorano)borazinium-Monokation [H3B3(NPEt3)3Cl2]+. Kristallstrukturen von Me3SiNPR3 · BH3 (R = Et,Ph), [H3B3(NPEt3)3Cl1,85Br0,15]Br · CCl4 und des Hydrolyseproduktes NH4[B5O6(OH)4] · 2 H2O

On the Tri(phosphorano)borazinium Monocation [H₃B₃(NPEt₃)₃Cl₂]⁺. Crystal Structures of Me₃SiNPR₃ · BH₃ (R = Et, Ph), [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄, and of the Product of Hydrolysis NH₄[B₅O₆(OH)₄] · 2 H₂O The crystal structures of the donor-acceptor complexes of the silylated phosphanimines with borane which are suitable as educts for the synthesis of tri(phosphorano)borazinium ions, Me₃SiNPR₃ · BH₃ (R = Et, Ph), are described. After addition of CCl₄ the reaction of Me₃SiNPEt₃ with HBBr₂ · SMe₂ in CH₂Cl₂ leads to the tri(phosphorano)borazinium monocation [H₃B₃(NPEt₃)₃Cl₂]⁺, which is characterized crystallographically as [H₃B₃ · (NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄. It complements the series of the tri(phosphorano) cations [H₃B₃(NPEt₃)₃]³⁺ and [H₄B₃(NPEt₃)₃]²⁺ by the monocation. NH₄[B₅O₆(OH)₄] · 2 H₂O can be isolated as product of hydrolysis of the tri(phosphorano)borazinium ions; its crystal structure is redetermined, because in the literature it is based on a wrong space group. Me₃SiNPEt₃ · BH₃ ( 1 ): Space group P1, Z = 4, lattice dimensions at 213 K: a = 710.9(4), b = 1465.9(3), c = 1536.0(3) pm, α = 107.05°, β = 99.40(3)°, γ = 97.41(3)°; R = 0.0740. Me₃SiNPPh₃ · BH₃ ( 2 ): Space group P2₁/c, Z = 4, lattice dimensions at 203 K: a = 934.6(1), b = 1398.6(1), c = 1626.1(1) pm, β = 103.52(1)°; R = 0.0556. [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄ ( 3 ): Space group P2₁/n, Z = 4, lattice dimensions at 223 K: a = 1237.9(3), b = 1214.1(3), c = 2402.4(4) pm, β = 93.52(1)°. 3 holds a B₃N₃ six-membered ring in a distorted boat conformation. NH₄[B₅O₆(OH)₄] · 2 H₂O ( 4 ): Space group Aba2, Z = 4, lattice dimensions at 273 K: a = 1131.3(1), b = 1103.0(1), c = 923.0(1) pm; R = 0.0564.     

Neue Koordinations-Motive bei Cyclothiazeno-Komplexen von Molybdän und Wolfram. Die Kristallstrukturen von [{Mo(N3S2)(Cl)(OtBu)2}{Mo(O)(N3S2)(OtBu)}]2 und [W(N3S2)2(LiCl){N≡W(NPPh3)3}2]

New Coordination Motives at Cyclothiazeno Complexes of Molybdenum and Tungsten. Crystal Structures of [{Mo(N₃S₂)(Cl)(O^tBu)₂}{Mo(O)(N₃S₂)(O^tBu)}]₂ and [W(N₃S₂)₂(LiCl){N≡W(NPPh₃)₃}₂] The metalla cyclothiazeno complexes (Cyclo-1λ⁶-metalla-3,5-dithia-2,4,6-triazino complexes) [{Mo(N₃S₂)(Cl) · (O^tBu)₂}{Mo(O)(N₃S₂)(O^tBu)}]₂ ( 1 ) and [W(N₃S₂)₂(LiCl) · {N≡W(NPPh₃)₃}₂] ( 2 ) are formed from [MoCl₃(N₃S₂)]₂ and LiO^tBu in toluene, and from [WCl₃(N₃S₂)]₂ and LiNPPh₃ in THF, respectively. The complexes form moisture sensitive, black ( 1 ) or brown ( 2 ) crystals, which we characterized by crystal structure analyses. 1 · Toluene: Space group P 1, Z = 1, lattice dimensions at –83 °C: a = 934.2(1), b = 964.4(1), c = 1700.3(1) pm; α = 83.54(1)°, β = 78.35(1)°, γ = 71.56(1)°, R₁ = 0.0339. 2 · 1.625 Toluene · 0.75 THF: Space group P 1, Z = 4, lattice dimensions at –80 °C: a = 1313.8(1), b = 2896.8(2), c = 3384.9(3) pm; α = 82.42(1)°, β = 88.71(1)°, γ = 77.28(1)°, R₁ = 0.0603.