Unexpected fragmentation of the Fe3(CO)9(μ3-Se)(μ3-AsCH3) cluster core in the reaction with CpCo(CO)2: synthesis and structure of Fe3(CO)6(μ3-Se)(μ-AsCH3{CpFe(CO)2})2(μ-CO)

The [Fe₃(CO)₆(μ₃-Se)(μ-AsCH₃{CpFe(CO)₂})₂(μ-CO)] (Cp=η⁵-C₅H₅) cluster has been obtained by the reaction of [Fe₃(CO)₉(μ₃-Se)(μ₃-AsCH₃)] with [CpCo(CO)₂]. Its crystal and molecular structures have been determined by X-ray analysis.     

Synthesis,characterization and weak ferromagnetic coupling in [Cu2(μ3-CO3)(SCN)2(py)4]n

The crystal structure of a novel [Cu₂(μ₃-CO₃)(SCN)₂(py)₄]_n complex has been determined. It comprises of [CuCO₃Cu]_n infinite chains, running along the a-axis, and is in this aspect similar to the previously described [Cu(CO₃)(4-aminopyridine)₂]·H₂O complex. The FTIR spectrum of [Cu₂(μ₃-CO₃)(SCN)₂(py)₄]_n has been recorded and analyzed. A CuCO₃Cu intrachain coupling between Cu(II) atoms has been found to be responsible for the weak ferromagnetic properties of [Cu₂(μ₃-CO₃)(SCN)₂(py)₄]_n.     

Synthesis and X-ray characterization of the new pentanickel cluster cation [Ni5(μ5-S)(μ3-S)2(μ2-S)(μ-CH3COO)(PPh3)5]+

By reacting Ni(CH₃COO)₂·6H₂O with H₂S in the presence of PPh₃, the new Ni/S cluster of formula [Ni₅(μ₅-S)(μ₃-S)₂(μ₂-S)(μ-CH₃COO)(PPh₃)₅]PF₆·C₇H₈·0.5CH₂Cl₂ has been isolated and characterized by X-ray diffraction analysis. Crystal data: space group P2₁/c, a=15.774(4), b=21.235(7), c=29.288(7) Å, β=95.66(4)°. The inner core consists of a square pyramid of five nickel atoms, linked together by a bridging acetate and four variously bridging sulfur ligands. The ³¹P{¹H} NMR spectra in dichloromethane solution are consistent with the above geometry.     

铜(Ⅱ)配合物[Cu_3(μ-OH)(μ-pz)_3(Hpz)(μ-Ac)_2]_n的合成与晶体结构

吡唑与醋酸铜在p H 9的水溶液中,室温下通过自组装合成标题配合物。用元素分析和X-射线单晶衍射分析配合物的结构,结果显示,晶体属于单斜晶系,空间群为P2(1)/c,晶体单胞参数为a=11.648(2),b=19.869(3),c=9.703 5(16),β=99.535(2)°。配合物3个中心铜(Ⅱ)离子均采取四面体构型,氢氧根与3个铜离子均形成配位键,由于配体桥连使配合物形成螺旋链,螺旋链之间通过醋酸根连接。     

Ru4(μ-CO)(CO)9(η4-μ4-C6H4)(η2-μ1,μ4-PPhCH2CH2PPh2): an unusual pyrolysis product of Ru3(CO)10(dppe) containing a benzyne ligand

The thermal decomposition of Ru₃(CO)₁₀(dppe) in refluxing benzene gives, in contrast to the pyrolysis of the dppm analogue, the tetranuclear cluster Ru₄(μ-CO)(CO)₉(η⁴-μ₄-C₆H₄)(η²-μ₁,μ₄-PCH₂CH₂PPh₂) (1) along with Ru₃(CO)₉(η²-μ₁,μ₂-C₆H₅)(η³-μ₁,μ₂-PPhCH₂CH₂PPh₂) (2). The single-crystal structure analysis of 1 reveals a square-planar tetraruthenium skeleton containing a η⁴-μ₄-benzyne ligand as well as a η²-μ₁,μ₄-phosphinidene–phosphine ligand.     

Phosphorus–carbon bond cleavage of Ph2PCH2PPh2 at a triruthenium center: synthesis and structural characterization of [Ru3(μ-CO)(CO)6(μ-PPh2)2(μ3-CH2PPh)]

The reaction of Ph₂PH with [Ru₃(CO)₁₀(μ-dppm)] (1) at 98°C gave [Ru₃(μ-CO)(CO)₆(μ-PPh₂)₂(μ₃-CH₂PPh)] (7) in 20% yield. Compound 7 was characterized by elemental analysis, ¹H and ³¹P{¹H} NMR and mass spectroscopic data and also by a single crystal structure determination. The compound is shown to consist of a triruthenium cluster with an unusual example of a triply bridging CH₂PPh ligand and two doubly bridging PPh₂ ligands.     

A novel 3-D chiral coordination polymer: hydrothermal synthesis and structural characterization of [Co3(μ3-OH)(μ5-btc)(μ6-Hbtc)(H2O)3·6H2O]n

A chiral 3-D open-framework coordination polymer [Co₃(μ₃-OH)(μ₅-btc)(μ₆-Hbtc)(H₂O)₃·6H₂O]_n was successfully obtained from the mixture of Co(CH₃COO)₂·4H₂O, H₃btc (where H₃btc=benzene-1,2,4-tricarboxylic acid), NaOH and H₂O under hydrothermal condition, which contains a novel and unprecedented coordination mode of btc (see Scheme 1

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Scheme 1. Coordination modes of btc in the compounds having been synthesized. I, μ₄-btc (in the literature [9]); II, μ₆-btc and III, μ₅-btc (see this paper).

).     

A novel 3D coordination polymer [Cd15(μ4-Mtta)12(μ3-Mtta)6(μ3-SO4)4(μ3-OH)4]: Synthesis,structure and solid properties

A 3D coordination polymer, {[Cd₁₅(μ₄-Mtta)₁₂(μ₃-Mtta)₆(μ₃-SO₄)₄(μ₃-OH)₄] · 6H₂O}_n (1) (Mtta = 5-methyl-tetrazolate), which shows the rare multifunction of in situ formed Mtta and bright photo-induced blue emission, was isolated from a hydrothermal reaction of CdSO₄ · 8/3H₂O, NaN₃ in acetonitrile and water.     

Synthesis and Crystal Structure of [Pb(phen)(μ-N3)(μ-NO3)]n and Its Thermal Decomposition to PbO Nanoparticles

Nano rods of a new 1D polymeric lead(II) complex containing the Pb₂-(μ-N₃)₂ motif, [Pb(phen)(μ-N₃)(μ-NO₃)]_n (phen?=?1,10-phenanthroline), has been synthesized by a sonochemical method. The new nano-structure was characterized by scanning electron microscopy, X-ray powder diffraction, elemental analyses and IR spectroscopy. A single crystalline material was obtained by applying a heat gradient to a solution of reagents. The single crystal X-ray data showed the coordination number of the Pb²⁺ ions to be eight (PbN4O4), with the Pb²⁺ ions having “stereo-chemically active” electron lone pairs; the coordination sphere was hemidirected. The chains of [Pb(phen)(μ-N₃)(μ-NO₃)]_n interact with each other via π–π interactions to create a 3D framework. PbO nanoparticles were obtained by thermolysis of 1 at 180?°C with oleic acid as a surfactant. The average diameter of the nanoparticles was estimated to be 33?nm by the Scherrer equation. The morphology and size of the prepared PbO samples were further observed using SEM.     

A new eight-connected net with CsCl-type topology built on unique [Co2(μ3-OH)(μ2-OH2)(CO2)3]2 building blocks

A new metal-organic framework (MOF) [Co₂(μ₃-OH)(μ₂-OH₂)(oba)(Hoba)(pyz)]_n(1), (oba = 4,4’-oxybis(benzoate), pyz = pyrazine) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermal gravimetric analysis, elemental analysis, and magnetic techniques. The framework defines an eight-connected CsCl net with 4²⁴·6⁴ topology symbol. To the best of our knowledge, this is the first eight-connected CsCl-type net built on unique [Co₂(μ₃-OH)(μ₂-OH₂)(CO₂)₃]₂ molecular building blocks (MBBs).     

New Flower-Shaped Lead(II) Coordination Polymer at the Nano Scale: Synthesis, Structural Characterization and DFT Calculations of [Pb(o-phen)(N3)2] n Containing the Pb-(μ1,1-N3)(μ1,3-N3) Motif

A new nano-flower lead(II) azido coordination polymer from the ligand, orthophenanthroline (o-phen), [Pb(o-phen)(μ_1,1-N₃)(μ_1,3-N₃)] _n (1), was synthesized by a sonochemical method. Compound 1 was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), elemental analyses and IR spectroscopy. Single crystalline material was obtained using a heat gradient applied to a solution of the reagents. The structure of 1 is a coordination polymer of lead(II) containing the Pb-(μ_1,1-N₃)(μ_1,3-N₃) motif, formed of one-dimensional chains. The structure of the 1 was optimized by density functional theory. Structural parameters and IR spectra for 1 are consistent with the crystal structure. Pure phase PbO nanoparticles were obtained by thermolysis of 1 with oleic acid as a surfactant at 180 and 200 °C an air. PbO nanoparticles were characterized by XRD and SEM.     

Reactivity of [Ru3(μ-H)(μ-Me2pz)(CO)10] with 2,4-hexadiyne. Characterization of the first tetranuclear ynenyl complex

The tetranuclear ynenyl complex [Ru₄(μ-η²-Me₂pz)(μ₄-η⁴-MeCHCCCMe)(μ-CO)(CO)₁₀] (Me₂pz=3,5-dimethylpyrazolate) has been prepared by reaction of [Ru₃(μ-H)(μ-η²-Me₂pz)(CO)₁₀] with 2,4-hexadiyne and has been characterized by X-ray diffraction methods. It consists of an unusual broken-wing butterfly (spiked triangle) tetraruthenium framework (64-electron) with all the metal atoms bridged by a hex-2-yn-4-en-4-yl ligand (7-electron donor). This type of coordination is unprecedented for ynenyl ligands.     

Eu5(μ4-OH)(μ3-OH)4(μ-DBM)4(DBM)6 (DBM=dibenzoylmethide): a novel Eu5 square-pyramid polynuclear complex with a rare μ4-OH bridging mode

The reaction of EuOCl (EuCl₃) with dibenzoylmethane (HDBM) in the presence of N-methylmorpholine yields a novel Eu₅ square-pyramid polynuclear complex with a rare μ₄-OH bridging mode, Eu₅(μ₄-OH)(μ₃-OH)₄(μ-DBM)₄(DBM)₆ (1). The compound was characterized by elemental analysis, IR, fluorescence and Mössbauer spectra as well as by an X-ray single crystal structure determination. Crystallographic data for 1, C₁₅₀H₁₁₅Eu₅O₂₅, monoclinic, P2₁/c, a=22.223(5), b=17.427(1), c=35.708(5) Å, β=100.11(2)°, V=13614(4) ų, Z=4, R₁=0.0979, wR₂=0.1695.     

Thermal dehydration of Y(TFA)3(H2O)3: Synthesis and molecular structures of [Y(μ,η1:η1-TFA)3(THF)(H2O)]1∞ · THF and [Y4(μ3-OH)4(μ,η1:η1-TFA)6(η1-TFA)(η2-TFA)(THF)3(DMSO)(H2O)] · 6THF (TFA = trifluoroacetate)

In order to obtain a better anhydrous precursor for various applications in materials science and catalysis, thermal dehydration reactions of Y(TFA)₃(H₂O)₃ (TFA = trifluoroacetate) (A) were investigated. Thermal treatment of A at different temperatures under vacuum (5 × 10^?2 mm) for several hours failed to give totally anhydrous yttrium trifluoroacetate (as indicated by IR). Two different complexes, a partially dehydrated [Y(μ,η¹:η¹-TFA)₃(THF)(H₂O)]_1∞·THF (1) and a partially hydrolyzed [Y₄(μ₃-OH)₄(μ,η¹:η¹-TFA)₆(η¹-TFA)(η²-TFA)(THF)₃(DMSO)(H₂O)] · 6THF (2), were obtained with good and moderate yield, respectively, by crystallization of two different thermally treated batches of A from THF (or THF + DMSO) at room temperature. More efficient dehydration of A could be achieved at 200 °C in a furnace, the obtained anhydrous yttrium tris-trifluoroacetate giving Y(TFA)₃(THF)₂ (3) on crystallization from THF. All the products were characterized by elemental analyses, FT-IR and ¹H NMR spectroscopy as well as thermo-gravimetric analysis. In addition, single crystal X-ray structures are reported for 1 and 2, which show either a terminal (η¹ and η²) or bridging (μ,η¹:η¹) bonding behavior of the TFA ligand.     

Solvent/C60 exchange on Ir(CO)(PPH3)2(Cl)(η2-C60) and solvent/solvent’ exchange on Ir(CO)(PPH3)2(Cl)(solvent)

Dissociation of C₆₀ from Ir(CO)(PPh₃)₂(Cl)(η²-C₆₀) in a binary mixture of solvents (solvent₁ and solvent₂) produced non-equilibrium mixtures of Ir(CO)(PPh₃)₂(Cl)(solvent₁) and Ir(CO)(PPh₃)₂(Cl)(solvent₂). Once the solvated species were produced, they underwent a relative fast solvent exchange between them to produce an equilibrium mixture.     

[Y2(H2O)(BDC)3(DMF)]·(DMF)3: A rare 2-D (42.6)(45.6)2(48.62)(49.65.8) net with multi-helical-array and opened windows

In this work, we present a rare earth metal–organic framework, Y₂(H₂O)(BDC)₃(DMF)]·(DMF)₃ (BDC = 1,3-benzenedicarboxylate) 1, with a rare 2D (4².6)(4⁵.6)₂(4⁸.6²)(4⁹.6⁵.8) net, helical tubes with opposite chirality interweaving of triple-helical chains, opened windows and high thermal stability.     

硅氧烷表面活性剂(Ⅳ)(续3)涂料添加剂

在涂料生产和加工过程中，作为助剂的硅氧烧表面活性剂，即可作为流动改善剂、润湿剂、防滑剂、防刮痕剂和脱气剂，又在新涂料系列配方中成为不可缺少的助剂。由此，它们可通过改性来适应各种应用的需要。