胍基稀土配合物[(CH2)5NC(NiPr)2]3Yb的合成及晶体结构

胍基可以通过改变氮上的取代基来调控配合物的空间及电荷效应,它们作为辅助配体用于稀土金属配合物的合成得到了人们的广泛关注。本文通过胍基锂盐和无水YbCl3以3：1的摩尔比进行复分解反应,合成了均配型稀土化合物[(CH2)5NC(N^iPr)2]3Yb,测得它为正交品系,     

Synthesis and structures of new metallocene derivatives of lanthanides. Molecular structures of the complexes (C13H9)2Eu(THF)2 and (C5Me4H)2YbI(THF)

The divalent europium bis-fluorenyl complex (C₁₃H₉)₂Eu(THF)₂ was synthesized by the metathesis reaction of EuI₂(THF)₂ with two equivalents of fluorenylpotassium and by the protolytic substitution of the naphthalene ligand in the (C₁₀H₈)Eu(THF)₂ complex using the reaction with fluorene. According to X-ray diffraction data, the complex displays a skewed sandwich structure, in which one fluorenyl ligand is η⁵-coordinated to the metal atom, whereas the η³-coordination mode makes a great contribution to the coordination of another ligand. The (C₅Me₄H)₂YbI(THF) complex was synthesized by the reaction of YbI₃(THF)₂ with two equivalents of (C₅Me₄H)K. The structure of the complex was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 530–534, March, 2008.     

Synthesis and crystal structure of gallosilicate- and aluminogermanate tetrahydroborate sodalites Na8[GaSiO4]6(BH4)2 and Na8[AlGeO4]6(BH4)2

Tetrahydroborate enclathrated sodalites with gallosilicate and aluminogermanate host framework were synthesized under mild hydrothermal conditions and characterized by X-ray powder diffraction and IR spectroscopy. Crystal structures were refined in the space group P-43n from X-ray powder data using the Rietveld method. Na₈[GaSiO₄]₆(BH₄)₂: a=895.90(1) pm, V=0.71909(3)×10⁻⁶ nm³, R_P=0.074, R_B=0.022, Na₈[AlGeO₄]₆(BH₄)₂: a=905.89(2) pm, V=0.74340(6)×10⁻⁶ nm³, R_P=0.082, R_B=0.026. The tetrahedral framework T-atoms are completely ordered in each case and the boron atoms are located at the centre of the sodalite cages. The hydrogen atoms of the enclathrated anions were refined on x, x, x positions, restraining them to boron-hydrogen distances of 116.8 pm as found in NaBD₄.The IR-absorption spectra of the novel phases show the typical bands of the tetrahedral group as found in the spectrum of pure sodium boron hydride.The new sodalites are discussed as interesting -containing model compounds which could release pure hydrogen.     

Postmetallocene lanthanide-hydrido chemistry: A new family of complexes [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] (Ln = Y, Nd, Sm, Gd, Yb) supported by guanidinate ligands-synthesis, structure, and catalytic activity in olefin polymerization

The new family of Lewis base free hydrido complexes of rare-earth metals supported by guanidinate ligands [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] (Ln = Y, Nd, Sm, Gd, Yb) was synthesized and structurally characterized. Single-crystal X-ray and solution NMR studies revealed that these complexes are dimeric in both solid state and in [D6]benzene. The dimeric hydrido complexes can adopt eclipsed (Nd, Sm, Gd) or staggered (Y, Yb, Lu) conformations depending on the metal-atom size. Catalytic activity of these [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] complexes in the polymerization of ethylene, propylene, and styrene has been investigated. Complexes of Sm and Y have high catalytic activity in ethylene polymerization (1268 and 442 g mmol(-1) atm(-1) h(-1), respectively).     

Theoretical Studies on Dehydrogenation Reactions in Mg2(BH4)2(NH2)2 Compounds

Borohydrides have been recently hightlighted as prospective new materials due to their high gravimetric capacities for hydrogen storage. It is, therefore, important to under-stand the underlying dehydrogenation mechanisms for further development of these ma-terials. We present a systematic theoretical investigation on the dehydrogenation mecha-nisms of theMg₂(BH₄)₂(NH₂)₂ compounds. We found that dehydrogenation takes place most likely via the intermolecular process, which is favorable both kinetically and thermo-dynamically in comparison with that of the intramolecular process. The dehydrogenation of Mg₂(BH₄)₂(NH₂)₂ initially takes place via the direct combination of the hydridic H in BH₄^- and the protic H in NH₂^-, followed by the formation of Mg-H and subsequent ionic recombination of Mg-H^δ- …H^δ+N.     

三维混合价态铜配位聚合物[Cu(Me_2dtc)_2(CuI)_3]_n的合成与晶体结构(英文)

A new three-dimensional copper dithiocarbamate-copper iodide coordination polymer [Cu(Me2dtc)2(CuI)3]n (Me2dtc=N,N-dimethyldithiocarbamate) was synthesized by reactions of Cu(OAc)2,NaI and Na(Me2dtc) in DMF solution,characterized by elemental analysis,IR spectrum,and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system,space group C2/c with a=1.293 89(17) nm,b=1.077 61(11) nm,c=1.456 05(17) nm,β=115.585 (4)°,V=1.831 1 (4) nm3,Z=4,Dc=3.175 g·cm-3,Mr=875.28,λ (Mo Kα)=0.071 073 nm,μ=10.082 mm-1,F(000)=1 604,the final R=0.029 5 and wR=0.081 7. A total of 2 083 unique reflections were collected,of which 1 918 with I2σ(I) were observed. The Cu atoms are Cu(Ⅰ)/Cu(Ⅱ) mixed-valence and they have two different coordinate geometries,namely planar square and tetrahedron. This three-dimensional structure consists of individual Cu(Me2dtc)2 molecules linking together CuI polymeric chains which run parallel to the [001] direction vis Cu-S bonds.     

A new versatile binuclear seven-coordinate complex of molybdenum(II), [(μ-Cl)2{Mo(μ-Cl)(SnCl3)(CO)3}2]

The two new seven-coordinate anionic complexes of molybdenum(II), binuclear [(μ-Cl)₂{Mo(μ-Cl)(SnCl₃)(CO)₃}₂]²⁻ and mononuclear [MoCl₃(GeCl₃)(CO)₃]²⁻, have been synthesized and characterized by single-crystal X-ray diffraction studies. The binuclear complex exhibits a unique mode of reactivity towards norbornene. In a strictly anhydrous atmosphere the binuclear complex effectively initiates the ring-opening metathesis polymerization reaction of norbornene, but in the presence of water norbornene is efficiently transformed to the binorbornyl ether (C₇H₁₁)₂O.     

Reactions of [(Me3Si)3CAlMe2] with substituted benzoic acids. Isolation of a rare organoalumoxane carboxylate

The reactivity of bulky tris(trimethylsilyl)methyl group substituted aluminum trialkyl [(Me₃Si)₃CAlMe₂·THF] (1) with a series of substituted benzoic acid derivatives has been investigated. An equimolar reaction of 4-methyl benzoic acid or 4-tert-butyl benzoic acid with 1 in toluene at 50 °C leads to the formation of cyclic dimeric aluminum carboxylates [(Me₃Si)₃CAl(Me)(μ-O₂CC₆H₄R)]₂ (R = Me 2; ^tBu 3). Reaction of 3,5-di-iso-propylsalicylic acid (H₂dipsa) with 1 leads to the exclusive isolation of a trimeric organoaluminum carboxylate [(Me₃Si)₃CAl(μ-dipsa)]₃ (4), in which each aluminum is bound to two carboxylates, a phenoxide, and an alkyl group and produce a 12-membered macrocycle. Deliberate, but controlled, introduction of water in the form of 3,5-di-tert-butyl salicylic acid monohydrate (H₂dtbsa·H₂O) in the reaction with 1 in toluene leads to the isolation of carboxylate [(Me₃Si)₃CAl(μ-O)(μ-Hdtbsa)}₂] (5) with a bicyclic structure. Compound 5 represents a rare example of an organoalumoxane carboxylate that simultaneously possesses alkyl, oxo, and carboxylate moieties on aluminum.     

Synthesis,spectroscopic characterisation,crystal and molecular structure of [ReOBr(quin-2-c)2] and [ReOCl(quin-2-c)2] complexes: DFT and TD-DFT calculations for [ReOBr(quin-2-c)2]

Novel [ReOX(quin-2-c)₂] complexes (X = Cl, Br; quin-2-c = quinoline-2-carboxylate ion) have been prepared by treatment of [ReOX₃(AsPh₃)₂] with an excess of quinoline-2-carboxylic acid in acetonitrile. The complexes were characterised structurally and spectroscopically. The electronic structure of [ReOBr(quin-2-c)₂] has been calculated with the density functional theory (DFT) method, and additional information about binding has been obtained by NBO analysis. The UV–Vis spectrum of [ReOBr(quin-2-c)₂] has been discussed on the basis of TD-DFT calculations.     

Structures, energy bands and conductivities of (Me3NEt)[Pd(dmit) 2]2 and (NEt4)[Pd(dmit) 2]2

The electrical conductive molecular crystals (Me₃NEt)[Pd(dmit) ₂]₂ and (NEt₄)[Pd (dmit) ₂]₂ (dmit = 4,5-dimercapto-1,3-dithiole-2-thione) have been prepared, and their crystal structures and conductivity-temperature curves have been determined. The fact that the conductivity at room temperature of (Me₃NEt)[Pd(dmit) ₂]₂ (σ = 58 Ω^-1 cm^-1) is much higher than that of (Net₄)-[Pd(dmit)₂]₂ (σ = 2.2 Ω^-1.cm^-1) has been rationally explained by the results of energy band calculations. (MeNEt₃)[Pd(dmit)₂]₂ belongs to monoclinic system, P2₁/m space group and (Net₄)[Pd (dmit)₂]₂ belongs to triclinic system, space group. The structural conducting component of the crystals is the planar coordinative anion [Pd(dmit)₂]^0.5- which forms the face-to-face dimmer. [Pd(dmit)₂]^- ₂These dimers have been further constructed to be a kind of two-dimensional (2-D) conductive molecular sheet by means of S_S intermolecular interactions. The tiny difference of the above 2-D molecular sheets of the two title crystals has resulted in one order of magnitude difference of conductivities.     

具有[344484]笼状结构单元的微孔磷酸镓Ga3P2O8(OH)3(H2O)的合成、晶体结构及表征

Open-framework metal phosphates have been the subject of intense research owing to their interesting structural chemistry and potential applications in catalysis and ion exchange. The gallium phosphate family has exhibits rich structural chemistry. A novel gallium phosphate Ga₃P₂O₈(OH)₃(H₂O)(GaPO-CJ36) has been prepared in a hydrothermal reaction system of GaO(OH)-H₃PO₄-Co(chxn)₃Cl₃-H₂O at 180 ℃ for 7 days. Single-crystal X-ray analysis shows that GaPO-CJ36 crystallizes in the P2₁/c space group with a=1.833 35(12) nm, b=0.503 94(3) nm, c=1.062 90(9) nm, V=0.982 01(12) nm³, and Z=4. The connection of GaO₂(OH)₃(H₂O) octahedra, PO₄ and GaO₄ tetrahedra through vertex oxygen atoms forms a three-dimensional open framework, which contains 8-ring channels along the [010] direction. Its structure is composed of interesting [3⁴4⁴8⁴] cages, which have not been found in known gallium phosphates. CSD: 416779.     

锡(Ⅳ)N,N-二取代荒酸配合物Ph3SnS2CN(CH3)C6H5、 Ph3SnS2CN(C4H8NH)和SnCl2(S2CNEt2)2的合成、表征及晶体结构

Three tin (Ⅳ) complexes with N,N-dialkyl dithiocarbamates Ph₃SnS₂CN(CH₃)C₆H₅ (1),Ph₃SnS₂CN(C₄H₈NH) (2) and Sn(Cl)₂(S₂CNEt₂)₂ (3) have been synthesized. The crystal structures have been determined by X-ray sin- gle crystal diffraction. A crystal of the complex 1 is triclinic with space group P1, a=0.9485(3)nm, b=1.0491(3)nm, c=1.3631(4)nm, α=70.996(4)°, β=72.294(4)°, γ=79.609(4)°, Z=2, V=1.2168(6)nm³, D_c=1.453g·cm^-3, μ=1.234mm^-1, R=0.0442, wR=0.0858. A crystal of the complex 2 is monoclinic with space group P2(1)/c, a=1.2214(2)nm, b=1.1651(2)nm, c=1.5769(3)nm,β=99.039(2)°, Z=2, V=2.2162(7)nm³, D_c=1.532g·cm^-3, μ=1.352mm^-1, R=0.0267, wR=0.0591. A crystal of the complex 3 is triclinic with space group P1, a=0.7179(2)nm, b=0.9256(3)nm, c=1.5327(5)nm,α=93.857(4)°,β=98.992(4)°, γ=109.481(4)°, Z=2, V=0.9405(5)nm³, D_c=1.717g·cm^-3, μ=2.076mm^-1, R=0.0263, wR=0.0662. In the complexes 1 and 2 the tin atoms rendered five-coordination in a distorted tigonal bipyramidal structure and in the complex 3 the tin atom rendered six-coordination in a distorted octahedron structure. CCDC: 1, 179918; 2, 180024; 3, 180004.     

Complexes of neodymium and dysprosium triiodides with amines. Molecular structures of the {Dy[Me2N(CH2)3NH2]8}I3, NdI3(PriNH2)4, and NdI3(PriNH2)5 complexes

The dissolution of DyI₂ in diamine Me₂N(CH₂)₃NH₂ (DMDA) is accompanied by the disproportionation of the salt, hydrogen evolution, and oxidation of Dy^II to Dy^III. The [Dy(DMDA)₈]I₃ complex (1) was isolated from the solution. The neodymium amide amine complex (PrⁱNH)NdI₂(IPA)₄ was produced by the reaction of NdI₂ with isopropylamine (IPA). The recrystallization of this complex from IPA afforded the NdI₃(IPA)₄ complex (2). The recrystallization of (PrⁱNH)NdI₂(IPA)₄ from a toluene-IPA mixture gave the complex with five amine ligands, NdI₃(IPA)₅ (3). The structures of compounds 1, 2, and 3 were established by X-ray diffraction. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1674–1679, September, 2007.     

New open-framework in the uranyl vanadates A3(UO2)7(VO4)5O (A=Li, Ag) with intergrowth structure between A(UO2)4(VO4)3 and A2(UO2)3(VO4)2O

New uranyl vanadates A₃(UO₂)₇(VO₄)₅O (M=Li (1), Na (2), Ag (3)) have been synthesized by solid-state reaction and their structures determined from single-crystal X-ray diffraction data for 1 and 3. The tetragonal structure results of an alternation of two types of sheets denoted S for _∞²[UO₂(VO₄)₂]⁴⁻ and D for _∞²[(UO₂)₂(VO₄)₃]⁵⁻ built from UO₆ square bipyramids and connected through VO₄ tetrahedra to _∞¹[U(3)O₅-U(4)O₅]⁸⁻ infinite chains of edge-shared U(3)O₇ and U(4)O₇ pentagonal bipyramids alternatively parallel to a- and b-axis to construct a three-dimensional uranyl vanadate arrangement. It is noticeable that similar _∞[UO₅]⁴⁻ chains are connected only by S-type sheets in A₂(UO₂)₃(VO₄)₂O and by D-type sheets in A(UO₂)₄(VO₄)₃, thus A₃(UO₂)₇(VO₄)₅O appears as an intergrowth structure between the two previously reported series. The mobility of the monovalent ion in the mutually perpendicular channels created in the three-dimensional arrangement is correlated to the occupation rate of the sites and by the geometry of the different sites occupied by either Na, Ag or Li. Crystallographic data: 293 K, Bruker X8-APEX2 X-ray diffractometer equipped with a 4 K CCD detector, MoKα, λ=0.71073 Å, tetragonal symmetry, space group P4¯m2, Z=1, full-matrix least-squares refinement on the basis of F²; 1,a=7.2794(9) Å, c=14.514(4) Å, R1=0.021 and wR2=0.048 for 62 parameters with 782 independent reflections with I?2σ(I); 3, a=7.2373(3) Å, c=14.7973(15) Å, R1=0.041 and wR2=0.085 for 60 parameters with 1066 independent reflections with I?2σ(I).     

Monocyclische organotri- und -tetrastibane: synthese von [(Me3Si)2CHSb]n (n = 3, 4)

Reduction of (Me₃Si)₂CHSbCl₂ with Mg in tetrahydrofuran yields [(Me₃Si)₂CHSb]_n (n = 3, 4).     

Crystallographic report: Crystal structure of a homoleptic lanthanide guanidinate complex: [Ph2NC(NCy)2]3Yb·2PhCH3

The title complex, [Ph₂NC(NCy)₂]₃Yb·2PhCH₃ is a monomer with a six‐coordinate ytterbium center ligated by six nitrogen atoms of three chelating bidentate guanidinate ligands. The coordination geometry around the lanthanide ion is best described as a distorted trigonal prism. Copyright © 2005 John Wiley & Sons, Ltd.     

1,3-Migration of a phenyl group in the conversion of (Me3Si)2(PhMe2Si)CSiMePhX into (Me3Si)2(Ph2MeSi)CSiMe2Y species

The finding that compounds of the type (Me₃Si)₂(PhMe₂Si)CSiMePhX react with electrophiles to give very predominantly rearranged products (Me₃Si)₂(Ph₂MeSi)CSiMe₂Y, which would be expected to be thermodynamically disfavoured, can be rationalized in terms of a mechanism in which the anchimerically-assisted departure of X⁻ gives the Ph-bridged cation [(Me₃Si)₂

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MePh]⁺ which is attacked by the nucleophile at the less hindered centre bearing two Me groups rather than that bearing one Me and one Ph group, with the outcome determined by kinetic rather than thermodynamic factors. Both (Me₃Si)₂(Ph₂MeSi)CSiMe₂Br and its isomer (Me₃Si)₂(PhMe₂Si)CSiMePhBr react with AgBF₄ in CH₂Cl₂ or Et₂O to give >95% of the fluoride (Me₃Si)₂(Ph₂MeSi)CSiMe₂F. Reaction of the bromide (Me₃Si)₂(PhMe₂Si)CSiMePhBr with AgO₂CCF₃ in Et₂O, and that of the hydride (Me₃Si)₂(PhMe₂Si)CSiMePhH with ICl in CCl₄, likewise give >95% of the rearranged (Me₃Si)₂(Ph₂MeSi)CSiMe₂O₂CCF₃ and (Me₃Si)₂(Ph₂MeSi)CSiMe₂Cl, respectively.     

稀土配合物[Nd(o-NO2-C6H4COO)3(DMF)2]2的合成及其晶体结构

合成了一种新的双核倒反中心的稀土钕配合物[Nd(o-NO₂-C₆H₄COO)₃(DMF)₂]₂. 通过元素分析, 核磁共振谱和红外光谱对配合物的组成和结构进行了表征, 用热重分析研究了该配合物的热稳定性, 用X射线单晶衍射法测定了其晶体的结构. 钕配合物[Nd(o- NO₂-C₆H₄COO)₃(DMF)₂]₂晶体属三斜晶系, 空间群P-1, 晶胞参数a＝1.18652(12) nm, b＝1.24784(13) nm, c＝1.29958(13) nm, α＝64.220 (1)°, β＝66.306 (1)°, γ＝71.825 (1)°, V＝1.5645 (3) nm³, D_c＝2.167 mg/m³, Z＝2, μ＝3.415 mm^－1, F(000)＝986. 配合物中每个Nd(Ш)被4个邻硝基苯甲酸根桥联, Nd(Ш)的配位数为8, 配位原子分别来自于5个邻硝基苯甲酸羧酸根的6个氧原子和2个DMF的羰基氧原子. 配合物中的氢键和π…π 堆积作用使其成为三维立体结构. 同时发现了标题配合物固体具有光致发光现象, 发光性能测试表明该配合物具有很好的荧光性质.     

Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2''''-bpy)3]2[Co(2,2''''-bpy)2Cl][Co(2,2''''-bpy)2]H2-[SbW18O60]·4H2O

A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9-, formulated [Co(2,2'-bpy)3]2[Co(2,2'-bpy)2Cl][Co(2,2'-bpy)2]H2[SbW18O60]·4H2O (2,2'-bpy= 2,2(-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2'-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9- encapsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoⅡ and low-spin CoⅡ ions coexist in the title compound. Magnetic properties indicate that the compound is antiferromagnetic.     

Rh2(μ-SC6H5)2(CO)4的合成和晶体结构

一种路易斯碱，例如膦（PR3）或异氰化物（CNR）加到双核或多核络合物中，会导致低核物种的形成，这就伴随有金属一金属键的断裂[1]．这样的例子很多，如我们曾用F33（CO）12与P（SC6H5）3反应，分离出三个不同的两核铁数合物[2]．现在我们报导另一个例子：用Rh4（CO）12与P（SC6H小反应，同样也得到一个两核物种WhZ（P－SC6H巾（C）4．该化合物首先由B0ltoll＊等人用WhZ（CO）ZC12与苯硫酚C6H。SH反应得到，但有关它的X－rar晶体结构的测定还未见报导·与之相似的化合物Rh。（p－SC。H。F）。门O）。的结构已由ClaverN…