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…     

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     

Transition metal complexes of the tripodal ligand 4-(2′-pyridylmethyl)-4-azaheptane-1,7-diamine. Crystal structures of [CuLCl]ClO4 and [NiL(MeCN)2](ClO4)2

The tripodal ligand 4-(2′-pyridylmthyl)-4-azaheptane-1,7-diamine has been prepared by reaction of 2-aminemethyl pyridine with acrylonitrile, followed by the reduction of the nitrile groups. Copper(II), nickel(II), zinc(II), cobalt(III) and chromium(III) complexes of the ligand have been prepared and characterized and the crystal structures of the complexes [CuLCl]ClO₄ and [NiL(MeCN)₂](ClO₄)₂ determined. The copper complex is five coordinate with approximate square pyramidal stereochemistry with the apical position occupied by a primary amine donor. The nickel complex is octahedral with the pyridine nitrogen donor lying trans to an acetonitrile ligand.     

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.     

Complexes of N,N′,N′′-tris(2-hydroxypropyl)-1,4,7-triazacyclononane (L): Structures of [CuL](ClO4)(NO3), [CoL](ClO4)2, [ZnL](ClO4)2 and the catalytic activity of [MnL](ClO4)2 towards olefin epoxidation with hydrogen peroxide

Complexes of N,N′,N′′-tris(2-hydroxypropyl)-1,4,7-triazacyclononane (L), [CuL](ClO₄)(NO₃) (1), [CoL](ClO₄)₂ (2), [ZnL](ClO₄)₂ (3) and [MnL](ClO₄)₂ (4), have been synthesized and characterized on the basis of elemental analysis, electrospray ionization mass spectrometry, UV–Vis measurements and cyclic voltammetry. Crystal structures of the former three complexes, characterized by X-ray crystallography, show that these complexes are monoclinic with space group P2₁/n and P2₁/c. Each metal central in the complexes is six-coordinate with three N atoms of the macrocycle and three O atoms from the pendant hydroxypropyl arms, forming a distorted octahedral configuration. [MnL](ClO₄)₂ (4) is employed as catalyst in olefin epoxidation with H₂O₂. The final results indicate that complex (4) has good catalytic activity towards olefin epoxidation. Under mild conditions, the olefin conversion is moderate and epoxidation selectivity is 95–100%.     

A novel three-dimensional malonate-bridged complex {[Cu4(4,4′- bpy)8(mal)2(H2O)4](ClO4)2(H2O)4(CH3OH)2}n

A novel malonate-bridged copper (II) compound of formula {[Cu₄(4,4′-bpy)₈(mal)₂(H₂O)₄](ClO₄)₂(H₂O)₄(CH₃OH)₂}_n (4,4′-bpy = 4,4′-bipyridine; mal = malonate dianion) has been prepared and structurally characterized by X-ray crystallography. This compound exhibits a novel three-dimensional network being composed of Cu-4,4′-bipyridine layers which are pillared by malonate bridge ligands. The copper(II) ions has two different coordination environment.     

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.     

Phase transitions and molecular motions in [Ni(ND3)6](ClO4)2

[Ni(ND₃)₆](ClO₄)₂ has three solid phases between 100 and 300 K. The phase transitions temperatures at heating (T_C1^h=164.1 K and T_C2^h=145.1 K) are shifted, as compared to the non-deuterated compound, towards the lower temperature of ca. 8 and 5 K, respectively. The ClO₄⁻ anions perform fast, picosecond, isotropic reorientation with the activation energy of 6.6 kJ mol⁻¹, which abruptly slow down at T_C1^c phase transition, during sample cooling. The ND₃ ligands perform fast uniaxial reorientation around the Ni-N bond in all three detected phases, with the effective activation energy of 2.9 kJ mol⁻¹. The reorientational motion of ND₃ is only slightly distorted at the T_C1 phase transition due to the dynamical orientational order-disorder process of anions. The low value of the activation energy for the ND₃ reorientation suggests that this reorientation undergoes the translation-rotation coupling, which makes the barrier to the rotation of the ammonia ligands not constant but fluctuating. The phase polymorphism and the dynamics of the molecular reorientations of the title compound are similar but not quite identical with these of the [Ni(NH₃)₆](ClO₄)₂.     

Phase polymorphism of [Zn(DMSO)6](ClO4)2 studied by differential scanning calorimetry

Four solid phases of [Zn(DMSO)₆](ClO₄)₂ have been detected by differential scanning calorimetry (DSC). Specifically, the phase transitions were detected between: metastable phase KII ↔ supercooled phase K0 at , stable phase KIb ↔ stable phase KIa at , stable phase KIa ↔ stable phase K0 at . At T_m2 = 389 K crystals partially and at T_m1 = 465 K completely melts. From the entropy change values it was concluded that the phases: K0 and K0′ are the orientationally dynamically disordered phases, so called ODDIC crystals, and phases KIa, KIb and metastable KII are dynamically ordered but with some degree of positional disorder.     

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:

     

Synthesis, crystal structure and electrochemistry properties of [Cd(phen)(H2O)4](ClO4)Cl · H2O

A new inorganic-organic hybrid solid, [Cd(phen)(H₂O)₄](ClO₄)Cl · H₂O (phen = 1,10-Phenanthroline), has been synthesized under reflux conditions and characterized by single-crystal X-ray diffractions, ICP analysis, elemental analysis and electrical analysis. The compound crystallizes in the orthorhombic, space group a = 0.88361(10) ?, b = 1.8492(2) ?, c = 2.2157(2) nm, Z = 8, Dc = 1.899 g cm⁻³. Furthermore, electrical studies for complex have also been reported in this article.     

Synthesis and characterization of the [Cu(Cin2bda)2]ClO4 and [Cu(Ncin2bda)2]ClO4 complexes: Crystal structure of [Cu(Ncin2bda)2]ClO4

Two copper(I) complexes [Cu(Cin₂bda)₂]ClO₄ (I) and [Cu(Ncin₂bda)₂]ClO₄ (II) have been prepared by the reaction of the ligands N²,N²′-bis(3-phenylallylidene)biphenyl-2,2′-diamine (L¹) and N²,N²′-bis[3-(2-nitrophenyl)allylidene]biphenyl-2,2′-diamine (L²) and copper(I) salt. These compounds were characterized by CHN analyses, ¹H NMR, IR, and UV-Vis spectroscopy. The C=N stretching frequency in the copper(I) complexes shows a shift to a lower frequency relative to the free ligand due to the coordination of the nitrogen atoms. The crystal and molecular structure of II was determined by X-ray single-crystal crystallography. The coordination polyhedron about the copper(I) center in the complex is best described as a distorted tetrahedron. A quasireversible redox behavior was observed for complexes I and II. The article is published in the original.     

[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

[Gd2(Gly)6(H2O)4](ClO4)6(H2O)5的合成、晶体结构与热化学研究

利用微波技术合成了配合物[Gd₂(Gly)₆(H₂O)₄](ClO₄)₆(H₂O)₅, 进行了化学成分分析、红外表征和热重分析. 应用X衍射仪测定其晶体结构, 该晶体为一维链结构, 属三斜晶系, P 空间群, 晶胞参数: a＝1.1569(17) nm, b＝1.4138(2) nm, c＝1.5642(2) nm, α＝96.910(2)°, β＝102.735(2)°, γ＝105.512(2)°, V＝2.3606(6) nm³, Z＝2, D_c＝2.144 g•cm^－3. 采用精密溶解-反应量热计, 通过设计热化学循环, 计算出了该配合物的标准摩尔生成焓为 －(7960.73±3.23) kJ•mol^－1.     

Calorimetric study and thermal analysis of [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O and [ErY(Gly)6(H2O)4](ClO4)6·5H2O (Gly: glycin)

Two solid-state coordination compounds of rare earth metals with glycin, [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O and [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O were synthesized. The low-temperature heat capacities of the two coordination compounds were measured with an adiabatic calorimeter over the temperature range from 78 to 376 K. [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O melted at 342.90 K, while [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O melted at 328.79 K. The molar enthalpy and entropy of fusion for the two coordination compounds were determined to be 18.48 kJ mol⁻¹ and 53.9 J K⁻¹ mol⁻¹ for [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O, 1.82 kJ mol⁻¹ and 5.5 J K⁻¹ mol⁻¹ for [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O, respectively. Thermal decompositions of the two coordination compounds were studied through the thermogravimetry (TG). Possible mechanisms of the decompositions are discussed.     

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) ?.     

新配合物[Cd(H2O)2(phen)2](PA)2的制备及晶体结构

The new compound was prepared by the reaction of Cd(ClO₄)₂·6H₂O,1,10-phenanthroline (phen)and picric acid (HPA)(ratio 1∶3∶2) in methanol-aqueous solution refluxing for 4 hours. The crystals used for X-ray analysis was obtained by slow evaporation of the solution at room temperature. The crystal compound is in triclinic with space group with a=1.1363(4)nm,b=1.2593(2)nm,c=1.3972(4)nm,α=93.97(2)?,β=100.84(3)?,γ=106.29(2)?,Z=2,V=1.8690(9)nm³,D_c=1.715g·cm^-3, μ(MoKα)=0.677mm^-1,F(000)=972,R=0.0907,wR=0.2240. In the complex, the Cd(Ⅱ) cation is octahedrally coordinated to two 1,10-phenanthroline ligands and two water molecules in cis disposition. As outer sphere, picrate anions are combined with inner by hydrogen bond and static electricity interaction.     

[Co(tp)2(Me3-en)]ClO4手性配位氮的翻转动力学研究

用高效液相色谱（HPLC）法测定了水溶液中碱催化下异构体－（差向立体异构体）：Δ（S）∧（R）和Δ（R）∧（S）－[Co(tp)2(Me3-en)]ClO4（tp:2-羟基－2,4,6－环庚三烯－1－酮负离子;Me3-en:N,N,N'-三甲基乙二胺）手性配位氮的翻转（差向立体异构体）速率常数kep(34.0 ℃）,研究结果发现,碱催化下手性配位氮的翻转作用具有二级反应动力学方程：v=kep[配合物][OH^-],[Co(tp)2(Me3-en)]ClO4的kep值比[Co(tp)2(Me3-en)]ClO4的kep值大一个数量级,Δ（R）∧（S）-异构体比Δ（S）∧（R）－异构体具有更大的手性配位氮翻转速率。     

Structure of Ba Na Ethylenediaminetetraacetatocobaltate(III) Perchlorate, Na[Ba6(H2O)25][Co(Edta)]4(ClO4)9 · 5H2O

Crystals with uncommon composition NaBa₆[Co(Edta)]₄(ClO₄)₉ · 30H₂O (Edta⁴⁻ is ethylenediaminetetraacetic acid anion) were obtained with the following unit cell parameters: a = 14.8513(9) Å, b = 26.2361(15) Å, c = 15.1789(9) Å, α = 91.661(7)°, β = 113.035(7)°, γ = 89.897(7)°, space group P1¯. Each complex anion [Co(Edta)]⁻ is bonded through the carboxyl O atoms to five Ba atoms to give three-dimensional framework in a crystal. One perchlorate ion forms Ba-O-Cl-O-Ba bridge between the Ba atoms; four ClO ₄ ⁻ ions are isolated, while the remaining four ions act as monodentate ligands at the Ba atoms. The water molecules (25 in sum) complete the coordination sphere of the Ba atoms to eight-, nine-, or ten-vertex polyhedron. Four water molecules are in the closest surrounding of the Na atom, one H₂O molecule is isolated.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 8, 2005, pp. 590–595.Original Russian Text Copyright © 2005 by Zabel, Poznyak, Pawlowski.