[Cu(HIm)2(PPh3)2](BF4)的合成与晶体结构

A Cu(Ⅰ) complex with mix ligands [Cu(HIm)₂(PPh₃)₂](BF₄) was synthesized and characterized by elemental analysis, IRspectroscopy and X-ray diffraction crystallography. The crystal belongs to monoclinic system and P2₁/c space group, with cell parameters, a=1.2836(3)nm, b=1.5089(3)nm, c=2.0661(4)nm, α=90°, β=101.464(4)°,γ=90°, V=3.9219(13)nm³, Z=4 and D_c=1.374mg·m^-3. The Cu(Ⅰ) is coordinated by two Patoms from triphenylphosphine and two Natoms from imidazole to form the distorted tetrahedral geometry.     

Phase transitions, structural changes and molecular motions in [Zn(NH3)4](BF4)2 studied by neutron scattering, X-ray powder diffraction and nuclear magnetic resonance

Nuclear magnetic resonance (¹H NMR and ¹⁹F NMR) measurements performed at 90-295 K, inelastic incoherent neutron scattering (IINS) spectra and neutron powder diffraction (NPD) patterns registered at 22-190 K, and X-ray powder diffraction (XRPD) measurements performed at 86-293 K, provided evidence that the crystal of [Zn(NH₃)₄](BF₄)₂ has four solid phases. The phase transitions occurring at: T_C3=101 K, T_C2=117 K and T_C1=178 K, as were detected earlier by differential scanning calorimetry (DSC), were connected on one hand only with an insignificant change in the crystal structure and on the other hand with a drastic change in the speed of the anisotropic, uniaxial reorientational motions of the NH₃ ligands and BF₄⁻ anions (at T_C3 and at T_C2) and with the dynamical orientational order-disorder process (“tumbling”) of tetrahedral [Zn(NH₃)₄]²⁺ and BF₄⁻ ions (at T_C1). The crystal structure of [Zn(NH₃)₄](BF₄)₂ at room temperature was determined by XRPD as orthorhombic, space group Pnma (No. 62), a=10.523 Å, b=7.892 Å, c=13.354 Å and Z=4. Unfortunately, it was not possible to determine the structure of the intermediate and the low-temperature phase. However, we registered the change of the lattice parameters and unit cell volume as a function of temperature and we can observe only a small deviation from near linear dependence of these parameters upon temperature in the vicinity of the T_C1 phase transition.     

Electron transfer rate and structure of [Fe2(bpmp)(ppa)2](BF4)2

Mixed-valence μ-phenolate-bis(μ-carboxylate) diiron(II, III) complex [Fe₂(bpmp)(ppa)₂](BF₄)₂ (1) is prepared. The temperature dependence of the M?ssbauer spectra of the complex 1 is measured. The M?ssbauer parameters of the complex 1 show the unusual increase of isomer shift and quadrupole splitting with an increase in temperature. The spectra are explained by the dynamic electronic states in which the valence states of two iron atoms in a molecule are 2.2 and 2.8 on the M?ssbauer time scale at 293 K. The single crystal X-ray structure of the complex 1 is determined at 133 K. The complex 1 crystallizes in the triclinic space group 1. Two iron atoms in the complex 1 are crystallographycally inequivalent.     

The thermal decomposition reactions of [Co(en)3](NO3)3 and [Co(en)3](HSO4)3

The thermal decomposition reactions were determined for [Co(en)₃](N0₃)₃ and [Co(en)₃(HSO₄)₃ in a dynamic nitrogen gas atmosphere and _vacuo, where en represents ethylenediamine. Data were obtained using thermogravimetry, DTA, thermomagnetic analysis, and mass spectrometry. The dissociation reactions in nitrogen were found to be as follows:

and

In vacuo, the dissociation process for [Co(en)₃](N0₃)₃ is the same as in nitrogen. Also, the decomposition of [Co(en)₃](HSO₄)₃ is the same except for the first step which is:

     

用T-jump/FTIR研究MnCP、NiCP和PbCP的快速热分解(英)

0IntroductionCarbohydrazideisahydrazinederivativewithwhitecrystalofstrongreducingbehaviors.Becauseithasmanycoordinationatoms(fournitrogenatomsandoneoxygenatom),carbohydrazidecan,therefore,beusedasmultidentateligand.Itscoordinationcom鄄poundiswidelyusedint…     

Crystal structure of [Cu(en)2](ReO4)2

At T = 150 K the crystal structure of [Cu(en)₂] (ReO₄)₂ (en is ethylenediamine) is studied: a = 6.6229(1) ?, b = 14.2968(3) ?, c = 7.4859(2) ?, β = 102.415(1)°, V = 692.24(3) ?,³, P2₁/c space group, Z = 2, d _x = 3.282 g/cm³. Packing of complex cations is shown to be single layered and pseudohexagonal. Perrhenate anions are located between these layers and additionally coordinate copper atoms with Cu...O distances being 2.504(3) ?.     

Synthesis and molecular structure of Ba5(μ5-OH)[μ3-OCH(CF3)2]4[μ2-OCH(CF3)2]4 [OCH(CF3)2](THF)4(H2O)·THF: a source of barium fluoride

The reaction between metallic barium and fluoroisopropanol or alcoholysis of [Ba(OPrⁱ)₂] produces a pentanuclear fluoroalkoxide. Its X-ray structure determination showed its formulation to correspond to Ba₅(μ₅-OH)[μ₃-OCH(CF₃)₂]₄[μ₂-OCH(CF₃)₂]₄ [OCH(CF₃)₂](THF)₄(H₂O)·THF. The metallic core is based on a square pyramid encapsulating an hydroxo ligand. In addition to the barium---alkoxide bonds [2.53(3)–2.86(3) Å] neutral O-donors, four THF [2.82(2)–2.86(3) Å] and one H₂O [2.79(3) Å] and secondary barium---fluorine interactions [2.99(2)–3.31(2) Å] ensure high coordination numbers, from 9 to 11 for the metal centers. Hydrogen bonding between the apical fluoroisopropoxide, the water molecule and one THF molecule, non-bonded to a metal center, accounts for the stability of the hydrate and illustrates the Lewis acidity of fluoroalkoxides. Thermal decomposition leads to BaF₂.     

Structures Of Tetraammine Salts [Pt(NH3)4](N03)2, [Pd(NH3)4](N03)2, and [Pd(NH3)4]F2 H20

This contribution presents the results of a single crystal X-ray diffraction study of three ammine complexes of bivalent platinum and palladium: [Pt(NH₃)₄](N0₃)2, [Pd(NH₃)₄](N0₃)₂ and [Pd(NH₃)₄]F₂H₂O. The first two compounds are isostructural; metal atoms are located on inversion centers, all other atoms are in general positions. A three-dimensional framework is built from planar-square complex cations and nitrate ions joined by N-H...O hydrogen bonds. In [Pd(NH₃)₄]F₂H₂O, palladium atoms, as in the previous cases, are located on inversion centers, while oxygen atoms of water molecules are on the two-fold symmetry axis. A network of strong N-H...F and O-H...F hydrogen bonds linking the cations, anions, and crystallization water molecules is present in the structure.     

Crystal structure of [Cu(NH3)4](ReO4)2

At T = 150 K, the crystal structure of [Cu(NH₃)₄](ReO₄)₂ is studied: a = 6.5167(3) ?, b = 6.7790(3) ?, c = 7.4627(3) ?, α = 67.336(1)°, β = 80.004(1)°, γ = 70.687(1)°, V = 286.70(2) ?³, P-1 space group, Z = 1, d _x = 3.661 g/cm³. We analyze the packing of ions using the translation sublattice isolation technique.     

Crystal structure of [Pd(P(i-Pr)3)2(acac)]BF4

A single crystal X-ray diffraction study is carried out for [Pd(P(i-Pr)₃)₂(acac)]BF₄, T = 150(2) K. Crystal data: a = 10.2935(4) ?, b = 11.3591(5) ?, c = 13.8728(6) ?, α = 89.154(2)°, β = 68.448(1)°, γ = 85.032(1)°, P-1 space group, V = 1502.75(11) ?³, Z = 2, d _x = 1.354 g/cm³.     

Non-equivalent water molecules in [Ni(H2O)6](ClO4)2 and in [Ni(D2O)6](ClO4)2 in the thermogravimetric investigations

The thermal decomposition of [Ni(H₂O)₆](ClO₄)₂ and [Ni(D₂O)₆](ClO₄)₂ were studied by thermogravimetric analysis (TG) and simultaneous differential thermal analysis (SDTA) at a constant heating rate. The gaseous products of the decomposition were on-line identified by a quadrupole mass spectrometer (QMS). In both cases the process of decomposition starts at ca. 410 K and is connected with removal of water molecules in a stepwise way; at the beginning the first water molecule is lost, then the second and at higher temperature the third one. The rest of the water molecules are lost in the temperature region of ClO₄⁻ decomposition. The energy of activation of the process was calculated in both cases.     

Joint x-ray and neutron diffraction structure analysis of [(μ-H)3Re3(CO)8{(EtO)2POP(OEt)2}2]

The compound [(μ-H)₃Re₃(CO)₈{(EtO)₂POP(OEt)₂}₂] crystallises in the monoclinic space group P2₁/c with a 18.053(6), b 16.211(5), c 14.800(3) Å, β = 102.41(2)°, and Z = 4. Simultaneous refinement of a single parameter set to fit 3212 X-Ray (sin θ/λ) > 0.352 Å⁻¹ and 1480 neutron data has led to final weighted residuals R_w(F) of 0.096 (X-Ray) and 0.095 (neutron). The molecule exhibits noncrystallographic C₂ symmetry, with two edges of the Re₃ triangle bridged by (OEt)₂POP(OEt)₂ ligands. The hydride ligands lie close to the trimetal plane with each hydride bridging an Re---Re vector. Average molecular parameters involving the hydride ligands are Re---H 1.812(17), Re---Re 3.282(17) Å, Re---H---Re 130(3) and H---Re---H 107.6(27)/dg. All eight carbonyl ligands are terminal, the ligand polyhedron being derived from that in H₃Re₃(CO)₁₂ by substitution of four axial carbonyls by two bidentate phosphite ligands.     

Synthesis, properties and structures of the two “electron rich” cobalt-sulphur clusters [Co6(μ3-S)8(PEt3)6]

The reaction of hydrogen sulphide with [Co(H₂O)₆](BF₄)₂ and triethylphosphine in the presence of sodium tetraphenylborate or tetrabutylammonium hexafluorophosphate gave the paramagnetic clusters [Co₆(μ₃-S)₈(PEt₃)₆](Y) (Y = BPh₄, (1), PF₆, (2)). These compounds can be easily reduced by sodium napthalenide to the diamagnetic species [Co₆(μ₃-S)₈(PEt₃)₆] · 2C₄H₈O (3). The molecular structures of 1 and 3 have been established by single-crystal X-ray diffraction methods. Crystal data: (1) space group P , a = 19.481(9), b = 15.562(7), c = 12.390(b) Å, α = 92.70(8), β = 94.50(7), γ = 94.10(9)°, Z = 2, (3) space group R , a = 11.780(6) Å, α = 92.50(7)°, Z = 1. Both structures were solved by the heavy atom method and refined by full-matrix least-squares techniques to the conventional R factors values of 0.050 for 1 and 0.044 for 3 on the basis of 4251 and 1918 observed reflections, respectively. The two clusters [Co₆(μ₃-S)₈)(PEt₃)₆]^1+,0 are isostructural, the inner core consisting of an octahedron of cobalt atoms with all the faces symmetrically capped by triply bridging sulphur atoms. Each metal centre is additionally linked to a triethylphosphine group so that each cobalt atom is co-ordinated by four sulphur atoms and one phosphorus in a distorted square pyramidal environment. The addition of one electron whilst leaving unchanged the geometry of the inner framework, induces small changes in the structural parameters, the average Co---Co and Co---P distances being 2.794 (3) and 2.162 (2) Å for 1 and 2.817 (3) and 2.138 (2) Å for 3 respectively. Electrochemistry in non-aqueous solvents shows the electron-transfer sequence

Full-size image (3K)

The tricationic species is stable only in the short time of cyclic voltammetric tests.     

Synthesis and thermodynamic properties of a metal-organic framework: [LaCu6(μ-OH)3(Gly)6im6](ClO4)6

A metal-organic complex, which has the potential property of absorbing gases, [LaCu₆(μ-OH)₃(Gly)₆im₆](ClO₄)₆ was synthesized through the self-assembly of La³⁺, Cu²⁺, glycine (Gly) and imidazole (Im) in aqueous solution and characterized by IR, element analysis and powder XRD. The molar heat capacity, C_p,m, was measured from T = 80 to 390 K with an automated adiabatic calorimeter. The thermodynamic functions [H_T − H_298.15] and [S_T − S_298.15] were derived from the heat capacity data with temperature interval of 5 K. The thermal stability of the complex was investigated by differential scanning calorimetry (DSC).     

The thermal dissociation of the [Co(en)3](SCN)3 and [Co(en)3]I3 complexes

The thermal dissociation of the [Co(en)₃](SCN)₃ and [Co(en)₃]I₃ complexes was studied by thermogravimetry, differential thermal analysis, thermomagnetic analysis, pyrolytic techniques, evolved gas analysis, and mass spectrometry, in vacuo and nitrogen atmospheres. It was found that the [Co(en)₃](SCN)₃ complex dissociated in four steps:

It was not possible to elucidate the intermediate compounds formed in the thermal dissociation of the [Co(en)₃]I₃ complex.     

[Cu(TO)2(H2O)4](PA)2的合成和晶体结构

[Cu(TO)₂(H₂O)₄](PA)₂ was prepared by mixing the aqueous solution of 1,2,4-triazol-5-one(TO) and Cu(PA)₂. The molecular structure and crystal structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is triclinic, space group with a=0.7321(1)nm,b=0.7474(2)nm,c=1.3649(3)nm;α=88.65(2)°,β=85.63(1)°,γ=63.35(1)°;V=0.6655(2)nm³,Z=1. The Cu²⁺ coordinated with two TO molecule through its 2-nitrogen atom and four water molecules and showed an octahedral configuration.     

二维网状配合物[Co(dimb)2(MeOH)2](ClO4)2的合成及晶体结构

设计并合成了一个含咪唑基团的柔性双齿配体:1,3-二(咪唑基-1′-甲基)-5-甲基苯(dimb)(1),并进行了 ¹H NMR和结构表征。通过dimb与高氯酸钴的反应,得到了一个新型的具有二维网状结构的配合物:[Co(dimb)₂(MeOH)₂](ClO₄)₂(2)。X-射线晶体结构测定表明,这两个化合物的晶体学参数分别为:配体(1)属单斜晶系, 空间群     

配合物[Mn(bipy)3](ClO4)2的晶体结构和热分析研究

The complex [Mn(bipy)₃]·(ClO₄)₂ was synthesied and characterized by X-ray diffraction. X-ray diffraction result for the single crystal showed that the crystal belongs to triclinic, space group P1, a=0.8123(2),b=1.1024(2), c=1.8646(4)nm,α=102.30(3)°,β=91.00(3)°,γ=99.69(3)°,V=1.6056(6)nm³,Z=2,D_c=1.494g·cm^-3. The thermal decomposition of [Mn(bipy)₃](ClO₄)₂ occurred in a three steps pattern. The reaction mechanism of the first step decomposition was deduced as n(1-α)[-ln(1-α)](n-1)/n with the activation energy of 130kJ·mol^-1.