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.     

Synthesis and structure of the pentanuclear mixed-metal cluster [Co4MoCp(μ3-SBut)(μ3-S)(μ3-CO)(μ-CO)2(CO)6]

The pentanuclear mixed-metal cluster [Co₄MoCp(μ₃-SBu^t)(μ₃-S)(μ₃-CO)(μ-CO)₂(CO)₆] (1) has been synthesised by reaction of [CoMoCp(CO)₇] with Bu^tSSBu^t. X-ray structural analysis identified an asymmetric unit with three cobalt atoms and one molybdenum forming an irregular tetrahedron while one cobalt–molybdenum edge is bridged by a cobalt atom. Crystal data: space group P2(1)/n, a=10.162(2), b=13.722(3), c=17.69(5) Å, β=91.44(2)°, Z=4.     

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.     

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.     

Bridge-splitting of trans-[PtCl2(η2-CH2CH2)]2 by weak nucleophiles: Crystal and molecular structure of trans-[PtCl2(η2-CH2CH2)(MeCN)]

Bridge-splitting of trans-[PtCl₂(η²-CH₂CH₂)]₂, 1, by L in dichloromethane yields trans-[PtCl₂(η²-CH₂CH₂)(L)] (L = THF, 2, or MeCN, 3) with bridge-splitting equilibrium constants of 0.0289 ± 0.0007 and 3601 ± 215 mol^?1 dm³, respectively, as determined by UV/Vis measurements. The reaction of 3 in MeCN with Cl^? is essentially quantitative. The crystal structure of trans-[PtCl₂(η²-CH₂CH₂)(CH₃CN)] is reported.     

A novel two-dimensional network self-assembled by the narrowest ladder cations [Cu(CH3COO)(bpe)(H2O)]nn+ containing the Cu2(μ-O)2 cores and the dimeric anions [Cu2(nta)2(bpe)]2− through hydrogen-bonding interaction

A novel complex [Cu(CH₃COO)(bpe)(H₂O)]_n·n/2[Cu₂(nta)₂(bpe)] ·6nH₂O) (bpe=trans-1,2-bis(4-pyridyl)ethylene) was synthesized and characterized. The molecule structure shows that it is composed of the ladder-like double chain cations [Cu(CH₃COO)(bpe)(H₂O)]_nⁿ⁺ and the dimeric anions [Cu₂(nta)₂(bpe)]²⁻. Through bridging oxygen atom of the acetate, the Cu₂ (μ-O)₂ core is formed. The ladder-like chain cation is the narrowest ladder [3.422(3) Å]. Two-dimensional undulating network is constructed by the cations and the dimeric anions through hydrogen-bonding interactions.     

Sulfur-assisted chloride and triphenylphosphine dissociation of palladium(II) complex [Pd(PPh3)2(η1-SCNMe2)(Cl)]. X-ray structures of [Pd(PPh3)2(η1-SCNMe2)(Cl)], [Pd(PPh3)(Cl)]2(μ,η2-SCNMe2)2, and [Pd(PPh3)2(η2-SCNMe2)][PF6]

Treatment of Pd(PPh₃)₄ with Me₂NC(S)Cl in dichloromethane at −20 °C produces the complex [Pd(PPh₃)₂(η¹-SCNMe₂)(Cl)], 2. Variable temperature ¹H and ³¹P{H} NMR experiments of complex 2 shows the dissociation of either the chloride or the triphenylphosphine ligand to form complex [Pd(PPh₃)₂(η²-SCNMe₂)][Cl], 3 or the dipalladium complex [Pd(PPh₃)Cl]₂(μ,η²-SCNMe₂)₂, 4. The reaction of complex 2 with NaPF₆ affords complex [Pd(PPh₃)₂(η²-SCNMe₂)][PF₆], 5. Complexes 2, 4, and 5 are characterized by X-ray diffraction analyses.     

[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.     

Synthesis and structural characterization of [(μ-H)Ru3(CO)8{μ-S(CH2)3SH}(μ-dppe)] and [Ru3(CO)5{μ2-S(CH2)3S}2(η2-dppe)] (dppe=Ph2PCH2CH2PPh2)

The reaction of 1,3-propanedithiol with [Ru₃(CO)₁₀(μ-dppe)] (2) at 66°C afforded the thiolate complexes [(μ-H)Ru₃(CO)₈{μ-S(CH₂)₃SH}(μ-dppe)] (6) and [Ru₃(CO)₅{μ₂-S(CH₂)₃S}₂(η²-dppe)] (7) in 25 and 23% yields respectively. Compound 6 is formed by simple oxidative addition of one of the S–H bonds of 1,3-propanedithiol while the structurally unique 7 consists of an open triruthenium cluster with four terminal and one asymmetrically bridged carbonyl groups, two doubly bridged propanedithiolate ligands and a chelating dppe ligand.     

Molecular structure of [In2(μ,η1-OR)(μ,η2-OR)(η2-OR)3(η1-OR)] R = C2H4NMe2, a pincer ligand

Functional indium [In(OR)₃]_m alkoxides (R = C₂H₄OMe, C₂H₄NMe₂) have been obtained by alcoholysis of In[N(SiMe₃)₂]₃ and characterised by elemental analysis, FT-IR and NMR spectroscopy. The 2-dimethylaminoethoxide was characterised by X-ray diffraction. It corresponds to the association of two InO₆ octahedra giving the unsymmetrical dimer [In₂(μ,η¹-OR)(μ,η²-OR)(η²-OR)₃(η¹-OR)] (2). 2 was used as a pincer ligand toward Cu(acac)₂.     

The first complex of the pentameric phosphazane macrocycle [{P(μ-NtBu)}2(μ-NH)]5 with a neutral molecular guest: Synthesis and structure of [{P(μ-NtBu)}2(μ-NH)]5(CH2Cl2)2

The reaction of [{P(μ-N^tBu)}₂(μ-NH)}₅I]⁻[Li(thf)₄]⁺([1 · I]⁻[Li(thf)₄]⁺) with NaOMe in CH₂Cl₂ gives the title compound [{P(μ-N^tBu)}₂(μ-NH)]₅(CH₂Cl₂)₂ [1 · (CH₂Cl₂)₂] the first adduct containing this type of macrocyclic phosph(III)azane host and a neutral guest.     

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).     

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。     

配合物[Co(phendione)(SO4)(H2O)]5H2O非等温热分解动力学

以热重-差热法(TG-DTG)为手段,研究配合物[Co(phendione)(SO4)(H2O)]·5H2O非等温热分解过程动力学.结果表明,标题配合物第一阶段热分解为相界控制反应(三维)机理,表观活化能为59.85KJ·mol-1,指前因子InA为16.36,反应速率方程为dα/dt=Ae-E(1-α)<2/3>.第...     

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.     

经由原位酰化反应获得的化合物[Pb_2(μ_6-H_2bbh)(μ_6-H_2bta)]_n的合成、结构与荧光性能研究

利用水热合成技术,经由原位酰化反应获得的合成了一新化合物[Pb_2(μ_6-H_2bbh)(μ_6-H_2bta)]_n(1),通过元素分析、红外、紫外和X-射线单晶衍射对其结构进行了表征。1为单斜晶系,C2/m空间群,a=1.0965(2)nm,b=1.0763(2)nm,c=0.80673(16)nm,β=94.01(3)°,V=0.9497(3)nm3,Z=8。同时也对其进行了荧光性质的测试。     

一种铜配位聚合物[Cu(C_6H_4NO_2)(μ-Cl)]_n的合成、晶体结构及热稳定性

以止血环酸和2-吡啶甲醛为反应底物,采用溶剂热法,合成了一种新颖的配位聚合物[Cu(C6H4NO2)(μ-Cl)]n(C6H4NO2H=2-吡啶甲酸)。利用红外光谱、X-射线单晶衍射、热重分析对配合物结构进行了表征。结果表明:配位聚合物为四方晶系,空间群为P 42/n,晶胞参数:a=9.774(4)?,b=9.774(4)?,c=15.029(6)?,V=1435.7(11)?3,Z=16。在配位聚合物中,每个Cu2+离子与来自两个2-吡啶甲酸的3个O原子和1个N原子及2个Cl原子配位形成畸变的八面体构型。此外,每2个Cu2+通过2个Cl原子桥联形成二维网格状结构,层与层之间又通过π-π堆积和氢键作用,把二维网格状结构进一步堆积成三维超分子结构,从而更加稳定了晶体结构。     

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).

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