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.     

Reactivity of [WCl(SnCl3)(CO)3(NCMe)2] towards tBuCCH.: X-ray crystal structure of [WCl(CO)(tBuCCH)(NCMe)(PPh3)2]2[SnCl6]

In the reaction of [WCl(SnCl₃)(CO)₃(NCMe)₂] with tert-butylacetylene the very labile bis(alkyne) complex [WCl(SnCl₃)(CO)(^tBuCCH)₂(NCMe)] has been observed as the major product by means of IR and NMR spectroscopy. The latter compound in reaction with two equivalents of PPh₃ in CH₂Cl₂ solution gives very poorly soluble purple crystals of the tungsten(II) cationic complex. The crystal structure of this compound consists of the discrete [SnCl₆]²⁻ anion, two independent [WCl(CO)(^tBuCCH)(NCMe)(PPh₃)₂]⁺ cations and four MeCN (solvent) molecules. This is the first crystallographically characterized cationic chlorocarbonyl complex of tungsten(II) containing a terminal alkyne as ligand.     

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.     

二甲基甲酰胺(DMF)水解抑制剂

筛选出能有效抑制二甲基甲酰胺（DMF）水解的有机化合物，讨论了体系中水含量（反应温度）、反应时间，该有机化合物用量对DMF水解的影响，研究结果表明，所选用的DMF水解抑制剂加入量为0．007ml%h^-1，使用DMF体系维持在碱性状态，能有效抑制DMF的水解。     

Synthesis of an osmafuran from photochemical hydrolysis of OsCl2(CHC(PPh3)C(O)-η2-CHCH2)(PPh3)2

The η²-alkene coordinated α,β-unsaturated ketone complex Os(CHC(PPh₃)C(O)-η²-CHCH₂)Cl₂(PPh₃)₂ (3) is very stable even at elevated temperature due to the strong steric hindrance effect of PPh₃ ligands. However, compound 3 in a chloroform solution can be almost quantitatively converted into the corresponding osmafuran [OsCl(CO)(PPh₃)₂(CHC(PPh₃)C(CH₃)O)]Cl (6) via hydrolysis of the η²-coordinated olefin under photochemical conditions. Osmafuran 6 has been characterized by single crystal X-ray diffraction analysis, NMR spectroscopy and elemental analysis data. The UV-induced reaction provides a new highly efficient method for preparation of osmafurans by hydrolysis of η²-α,β-unsaturated ketone complexes.     

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.     

合成R_3~(2 )R_2~(3 )(PO_4)_4系統陶瓷顏料

把石榴石化学式3RO·R_2O_3·3SiO_2作为合成该系统颜料的基础,式中,与磷酸碱性相同的酸根(SiO_2)~(4-)为等分子的(PO_4)~(3-)所取代。自然界中含磷的石榴石遇到很少,主要以含锰阳离子的RO基的锰鋁榴石形态存在。锰离子使矿物着成淡玫瑰色。     

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.     

添加剂对MoCl3(OC8H17)2-Al(OPhCH3)(i-Bu)2催化丁二烯聚合的影响

研究了3种添加剂对钼系催化丁二烯聚合活性和产物相对分子质量及其分布的影响.结果显示,3种添加剂都能使体系的聚合活性提高;加入方式以Al(OPhCH,3)(i-Bu)2-MoCl3(OC8H17)2-添加剂为好.三者对聚合物的1,2-结构含量均无太大影响.其中α-氯代甲基丙酸酯使产物相对分子质量下降、相对分子质量分布变宽,因此其可在适当范围内用作相对分子质量调节剂.     

聚丙烯聚乙烯共混研究(1)(2)

采用工业用注射机进行共混研究。得出在PP∶HDPE=75∶25时,共混物具有好的机械性能,并讨论了温度、转速对共混的影响。     

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。     

二甲基甲酰胺(DMF)腐蚀试验结果

(时八月)金属DMF%℃丈丈丈丈O︸二d︸曰甘nU﹄U 90甘5.上SUS 30475℃0。00010 .00010 .00010。0001<0 .0001<0 .0001<0 .0001<0 .00010 0 00。0001.0004。0003。0020.0001。0001.0001。0001。0001。0006。0004.0005153134124105153134124105153134124105153134124105.0001.0002.0002。0028。0001.0001.0001.0001。0001.0012.0011。00050 0 00八廿尸舀‘”nUnU︸U甘O口一勺55 410 0 00丈0 0 00丈八U 10八U几U00材Q﹄5有上铝﹄UO八甘0<0 0 00丈脱氧铜100 95 90 50二甲基甲酰胺(DMF)腐蚀试验结果…     

Synthesis,structure and properties of a new copper (II) complex, [Cu2(4,4′-bpy)5(H2O)4](ClO4)4(4,4′-bpy)(DMF)2(H2O)2

A new copper (II) complex with formula [Cu₂(4,4′-bpy)₅(H₂O)₄](ClO₄)₄(4,4′-bpy)(DMF)₂(H₂O)₂ has been synthesized by reaction of 4,4′-bpyridine (4,4′-bpy) with Cu(ClO₄)₂. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C–H?O bonds, anion?π and C–H?π interactions are also evident in the structure. The preliminary investigation on the thermal property of the complex is presented.     

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).     

[Re(NBH2SBH3)(Me2PhP)(Et2dtc)]2 — a novel rhenium dimer with the unusual bridging (NBH2SBH3)4− ligand

The title compound is formed during the reaction of [ReN(Me₂PhP)(Et₂dtc)₂] (Me₂PhP=dimethylphenylphosphine, Et₂dtc⁻=diethyldithiocarbamate) with excess BH₃ in tetrahydrofurane. Two Re^V atoms are linked by two (NBH₂SBH₃)⁴⁻ units which act as three-dentate ligands via N, S and H forming an eight-membered metallacycle with additional coordination of an hydrido H atom trans to the nitrogen atom. The ReN multiple bond length is 1.70(1) Å which is only slightly longer than in the starting compound [ReN(Me₂PhP)(Et₂dtc)₂] (1.666(6) Å).     

配合物Co_3(BTB)_2(H_2O)_5(DMF)_9的合成及其催化染料废水脱色性能研究

使用配体1,3,5-三(4-羧基苯基)苯(H_3BTB)通过水热法合成了配合物Co_3(BTB)_2(H_2O)_5(DMF)_9(用Co L表示),经红外光谱和元素分析进行了结构表征。将其用于催化过氧化氢脱色活性艳蓝KN-R,研究了双氧水浓度、催化剂浓度、温度和活性艳蓝KN-R的初始浓度对脱色效果的影响。研究表明,CoL表现出优异的催化脱色性能,在废水处理方面具有广阔的应用前景。     

新型稀土配合物Tb(bza)3(dpe)(H2O)3的表征及热分解动力学性质

合成了新型稀土固态配合物Tb（bza）3（dpe）（H2O）3[（Hbza=Benzoic acid,dpe=1,2-Di-（4-pyridyl）-ethylen]。通过元素分析和化学分析确定了配合物的组成,采用红外光谱等技术对配合物进行了表征,研究了配合物的荧光性能,用TG-DTG法研究了配合物的热分解行为,用非模型等转化率法研究了配合物热分解脱水过程的动力学,获得其表观活化能、指前因子数值范围、最概然机理函数和模型函数。     

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.