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1.
《无机化学与普通化学杂志》2018,644(15):833-837
In order to enhance the thermal stability of the barium salt of 5,5′‐bistetrazole (H2BT), carbohydrazide (CHZ) was used to build [Ba(CHZ)(BT)(H2O)2]n as a new energetic coordination compound by using a simple aqueous solution method. It was characterized by FT‐IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction. The crystal belongs to the monoclinic P21/c space group [a = 8.6827(18) Å, b = 17.945(4) Å, c = 7.2525 Å, β = 94.395(2)°, V = 1126.7(4) Å3, and ρ = 2.356 g · cm–3]. The BaII cation is ten‐coordinated with one BT2–, two shared carbohydrazides, and four shared water molecules. The thermal stabilities were investigated by differential scanning calorimetry (DSC) and thermal gravity analysis (TGA). The dehyration temperature (Tdehydro) is at 187 °C, whereas the decomposition temperature (Td) is 432 °C. Non‐isothermal reaction kinetics parameters were calculated by Kissinger's method and Ozawa's method to work out EK = 155.2 kJ · mol–1, lgAK = 9.25, and EO = 158.8 kJ · mol–1. The values of thermodynamic parameters, the peak temperature (while β → 0) (Tp0 = 674.85 K), the critical temperature of thermal explosion (Tb = 700.5 K), the free energy of activation (ΔG≠ = 194.6 kJ · mol–1), the entropy of activation (ΔS≠ = –66.7 J · mol–1), and the enthalpy of activation (ΔH≠ = 149.6 kJ · mol–1) were obtained. Additionally, the enthalpy of formation was calculated with density functional theory (DFT), obtaining ΔfH°298 ≈ 1962.6 kJ · mol–1. Finally, the sensitivities toward impact and friction were assessed according to relevant methods. The result indicates the compound as an insensitive energetic material. 相似文献
2.
《Journal of Coordination Chemistry》2012,65(7):553-562
Ligand substitution of trans-[CoIII(en)2(Me)H2O]2+ was studied for pyrazole, 1,2,4-triazole and N-acetylimidazole as entering nucleophiles. These displace the coordinated H2O molecule trans to the methyl group to form trans-[Co(en)2(Me)azole]. Stability constants at 18°C for the substitution of H2O by pyrazole, 1,2,4-triazole and N-acetylimidazole are 0.7 ± 0.1, 13.8 ± 1.4 and 1.7 ± 0.2 M?1, respectively. Second order rate constants at the same temperature for the reaction of trans-[CoIII(en)2(Me)H2O]2+ with pyrazole, 1,2,4-triazole and N-acetylimidazole are 161 ± 12, 212 ± 11 and 12.9 ± 1.6 M?1 s?1, respectively. Activation parameters (ΔH≠, ΔS≠) are 67 ± 6 kJ mol?1, + 27 ± 19 J K?1 mol?1; 59 ± 2 kJ mol?1, + 1 ± 6 J K?1 mol?1 and 72 ± 4 kJ mol?1, + 23 ± 14 J K?1 mol?1 for reactions with pyrazole, 1,2,4-triazole and N-acetylimidazole, respectively. Substitution of coordinated H2O by azoles follows an Id mechanism. 相似文献
3.
Bi‐Dong Wu Zun‐Ning Zhou Yan‐Gang Bi Li Yang Jian‐Guo Zhang Tong‐Lai Zhang 《无机化学与普通化学杂志》2013,639(5):799-803
The intriguing multi‐ligand compound [Cu(IMI)4Cl]Cl ( 1 ) with the ligand imidazole (IMI) was synthesized and characterized by elemental analysis and FT‐IR spectroscopy. The crystal structure was determined by X‐ray single crystal diffraction and the crystallographic data showed that the compound belongs to the monoclinic P21/n space group [α = 8.847(2) Å, b = 13.210(3) Å, c = 13.870(3) Å, and β = 90.164(3)°]. Furthermore, the CuII ion is five‐coordinated by four nitrogen atoms from four imidazole ligands and a chlorine atom. The thermal decomposition mechanism was determined based on differential scanning calorimetry (DSC) and thermogravimetric (TG‐DTG) analysis. The non‐isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa's method, respectively. The energy of combustion, enthalpy of formation, critical temperature of thermal explosion, entropy of activation (ΔS≠), enthalpy of activation (ΔH≠), and free energy of activation (ΔG≠) were measured and calculated. 相似文献
4.
V2O3(OH)4(g), Proof of Existence, Thermochemical Characterization, and Chemical Vapor Transport Calculations for V2O5(s) in the Presence of Water By use of the Knudsen-cell mass spectrometry the existence of V2O3(OH)4(g) is shown. For the molecules V2O3(OH)4(g), V4O10(g), and V4O8(g) thermodynamic properties were calculated by known Literatur data. The influence of V2O3(OH)4(g) for chemical vapor transport reactions of V2O5(s) with water ist discussed. ΔBH°(V2O3(OH)4(g), 298) = –1920 kJ · mol–1 and S°(V2O3(OH)4(g), 298) = 557 J · K–1 · mol–1, ΔBH°(V4O10(g), 298) = –2865,6 kJ · mol–1 and S°(V4O10(g), 298) = 323.7 J · K–1 · mol–1, ΔBH°(V4O8(g), 298) = –2465 kJ · mol–1 and S°(V4O8(g), 298) = 360 J · K–1 · mol–1. 相似文献
5.
The blue tetranuclear CuII complexes {[Cu(bpy)(OH)]4Cl2}Cl2 · 6 H2O ( 1 ) and {[Cu(phen)(OH)]4(H2O)2}Cl4 · 4 H2O ( 2 ) were synthesized and characterized by single crystal X‐ray diffraction. ( 1 ): P 1 (no. 2), a = 9.240(1) Å, b = 10.366(2) Å, c = 12.973(2) Å, α = 85.76(1)°, β = 75.94(1)°, γ = 72.94(1)°, V = 1152.2(4) Å3, Z = 1; ( 2 ): P 1 (no. 2), a = 9.770(3) Å, b = 10.118(3) Å, c = 14.258(4) Å, α = 83.72(2)°, β = 70.31(1)°, γ = 70.63(1)°, V = 1252.0(9) Å3, Z = 1. The building units are centrosymmetric tetranuclear {[Cu(bpy)(OH)]4Cl2}2+ and {[Cu(phen)(OH)]4(H2O)2}4+ complex cations formed by condensation of four elongated square pyramids CuN2(OH)2Lap with the apical ligands Lap = Cl, H2O, OH. The resulting [Cu4(μ2‐OH)2(μ3‐OH)2] core has the shape of a zigzag band of three Cu2(OH)2 squares. The cations exhibit intramolecular and intermolecular π‐π stacking interactions and the latter form 2D layers with the non‐bonded Cl– anions and H2O molecules in between (bond lengths: Cu–N = 1.995–2.038 Å; Cu–O = 1.927–1.982 Å; Cu–Clap = 2.563; Cu–Oap(OH) = 2.334–2.369 Å; Cu–Oap(H2O) = 2.256 Å). The Cu…Cu distances of about 2.93 Å do not indicate direct interactions, but the strongly reduced magnetic moment of about 2.74 B.M. corresponds with only two unpaired electrons per formula unit of 1 (1.37 B.M./Cu) and obviously results from intramolecular spin couplings (χm(T‐θ) = 0.933 cm3 · mol–1 · K with θ = –0.7 K). 相似文献
6.
The thermal behavior of Tb2 (p‐MBA)6(phen)2 (p‐MBA=p‐methylbenzoate; phen=1,10‐phenanthroline) in a static air atmosphere was investigated by TG‐DTG, SEM and IR techniques. The thermal decomposition of the Tb2(p‐MBA)6(phen)2 occurred in three consecutive stages at TP of 354, 457 and 595 °C. By Malek method, RO (n<1) was defined as kinetic model for the first‐step thermal decomposition. The activation energy (E) of this step is 170.21 kJ·mol‐1, the enthalpy of activation (ΔH≠) 164.98 kJ·mol‐1, the Gibbs free energy of activation (ΔG≠) 145.04 kJ·mol‐1, the entropy of activation (ΔS≠) 31.77 J·mol‐1·K‐1, and the pre‐exponential factor (A) 1015.21 s‐1. 相似文献
7.
Reactions of 1,10‐phenanthroline monohydrate, Na2C4H4O4 · 6 H2O and MnSO4 · H2O in CH3OH/H2O yielded a mixture of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O ( 1 ) and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) Å3, Z = 1) consists of the dinuclear [Mn2(H2O)4(phen)2(C4H4O4)2] molecules and hydrogen bonded H2O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H2O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) Å3, Z = 2) is composed of the [Mn(phen)2(H2O)2]2+ cations, [Mn(phen)2(C4H4O4)] complex molecules, (C4H4O4)2– anions, and H2O molecules. The (C4H4O4)2– anions and H2O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings. 相似文献
8.
L-脯氨酸独有的亚胺基使其在生物医药领域具有许多独特的功能,并广泛用作不对称有机化合物合成的有效催化剂。本文在碱性介质中研究了二(氢过碘酸)合银(III)配离子氧化 L-脯氨酸的反应。经质谱鉴定,脯氨酸氧化后的产物为脯氨酸脱羧生成的 γ-氨基丁酸盐;氧化反应对脯氨酸及Ag(III) 均为一级;二级速率常数 k′ 随 [IO4-] 浓度增加而减小,而与 [OHˉ] 的浓度几乎无关;推测反应机理应包括 [Ag(HIO6)2]5-与 [Ag(HIO6)(H2O)(OH)]2-之间的前期平衡,两种Ag(III)配离子均作为反应的活性组分,在速控步被完全去质子化的脯氨酸平行地还原,两速控步对应的活化参数为: k1 (25 oC)=1.87±0.04(mol·L-1)-1s-1,∆ H1≠=45±4 kJ · mol-1, ∆ S1≠=-90±13 J· K-1·mol-1 and k2 (25 oC) =3.2±0.5(mol·L-1)-1s-1, ∆ H2≠=34±2 kJ · mol-1, ∆ S2≠=-122 ±10 J· K-1·mol-1。本文第一次发现 [Ag(HIO6)2]5-配离子也具有氧化反应活性。 相似文献
9.
Khalid S. Khairou 《国际化学动力学杂志》2003,35(2):67-72
The kinetics of decomposition of an [Pect·MnVIO42?] intermediate complex have been investigated spectrophotometrically at various temperatures of 15–30°C and a constant ionic strength of 0.1 mol dm?3. The decomposition reaction was found to be first‐order in the intermediate concentration. The results showed that the rate of reaction was base‐catalyzed. The kinetic parameters have been evaluated and found to be ΔS≠ = ? 190.06 ± 9.84 J mol?1 K?1, ΔH≠ = 19.75 ± 0.57 kJ mol?1, and ΔG≠ = 76.39 ± 3.50 kJ mol?1, respectively. A reaction mechanism consistent with the results is discussed. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 67–72, 2003 相似文献
10.
SUBALA MONDAL SUMON RAY ANIMESH CHATTOPADHYAY DEBABRATA NANDI ROSHNI SARKAR ALAK KUMAR GHOSH 《国际化学动力学杂志》2014,46(10):587-596
The kinetics of the interactions between three sulfur‐containing ligands, thioglycolic acid, 2‐thiouracil, glutathione, and the title complex, have been studied spectrophotometrically in aqueous medium as a function of the concentrations of the ligands, temperature, and pH at constant ionic strength. The reactions follow a two‐step process in which the first step is ligand‐dependent and the second step is ligand‐independent chelation. Rate constants (k1 ~10?3 s?1 and k2 ~10?5 s?1) and activation parameters (for thioglycolic acid: ΔH1≠ = 22.4 ± 3.0 kJ mol?1, ΔS1≠ = ?220 ± 11 J K?1 mol?1, ΔH2≠ = 38.5 ± 1.3 kJ mol?1, ΔS2≠ = ?204 ± 4 J K?1 mol?1; for 2‐thiouracil: ΔH1≠ = 42.2 ± 2.0 kJ mol?1, ΔS1≠ = ?169 ± 6 J K?1 mol?1, ΔH2≠ = 66.1 ± 0.5 kJ mol?1, ΔS2≠ = ?124 ± 2 J K?1 mol?1; for glutathione: ΔH1≠ = 47.2 ± 1.7 kJ mol?1, ΔS1≠ = ?155 ± 5 J K?1mol?1, ΔH2≠ = 73.5 ± 1.1 kJ mol?1, ΔS2≠ = ?105 ± 3 J K?1 mol?1) were calculated. Based on the kinetic and activation parameters, an associative interchange mechanism is proposed for the interaction processes. The products of the reactions have been characterized from IR and ESI mass spectroscopic analysis. A rate law involving the outer sphere association complex formation has been established as 相似文献
11.
Cobalt Chelates for Hydrogenation Catalysts. II. Hydride Formation with [Co(dmgH)2] and [Co(dpnH)]+ In the presence of benzil as scavanger for the hydridocomplexes [Co(dpnH)]+ and [Co(dmgH)2] the hydride formation in water/n-propanol (50% v/v) becomes the rate determining step, and the ligand hydrogenation is completely suppressed in the case of [Co(dpnH)]+, but only partially in the case of [Co(dmgH)2]. The rate of hydride formation in both cases is 2nd order with respect to the complex, and the activation parameters ([Co(dmgH)2]: ΔH≠ = 48.4 ± 1.0 kJ · mol–1, ΔS≠ = ?57.4 ± 3.4J · mol?1 · K?1, [Co(dpnH)]+: ΔH≠ = 52.7 = 0.4 kJ · mol?1, ΔS≠ = ?59.8 ± 1.2J · mol?1 · K?1) indicate a H2-activation by homolytic splitting for both complexes. Some sources of error and possible causes for the missing activity of [Co(tim)]2+ are discussed. 相似文献
12.
Structure and Magnetic Properties of Bis{3‐amino‐1,2,4‐triazolium(1+)}pentafluoromanganate(III): (3‐atriazH)2[MnF5] The crystal structure of (3‐atriazH)2[MnF5], space group P1, Z = 4, a = 8.007(1) Å, b = 11.390(1) Å, c = 12.788(1) Å, α = 85.19(1)°, β = 71.81(1)°, γ = 73.87(1)°, R = 0.034, is built by octahedral trans‐chain anions [MnF5]2–∞ separated by the mono‐protonated organic amine cations. The [MnF6] octahedra are strongly elongated along the chain axis (<Mn–Fax> 2.135 Å, <Mn–Feq> 1.842 Å), mainly due to the Jahn‐Teller effect, the chains are kinked with an average bridge angle Mn–F–Mn = 139.3°. Below 66 K the compound shows 1D‐antiferromagnetism with an exchange energy of J/k = –10.8 K. 3D ordering is observed at TN = 9.0 K. In spite of the large inter‐chain separation of 8.2 Å a remarkable inter‐chain interaction with |J′/J| = 1.3 · 10–5 is observed, mediated probably by H‐bonds. That as well as the less favourable D/J ratio of 0.25 excludes the existence of a Haldene phase possible for Mn3+ (S = 2). 相似文献
13.
Reaction of CuCl2 · 2H2O, phenanthroline, maleic acid and NaOH in CH3OH/H2O (1:1 v/v) at pH = 7.0 yielded blue {[Cu(phen)]2(C4H2O4)2} · 4.5H2O, which crystallizes in the monoclinic space group C2/c (no. 15) with cell dimensions: a = 18.127(2)Å, b = 12.482(2)Å, c = 14.602(2)Å, β = 103.43(1)°, U = 3213.5(8)Å3, Z = 4. The crystal structure consists of the centrosymmetric dinuclear {[Cu(phen)]2(C4H2O4)2} complex molecules and hydrogen bonded H2O molecules. The Cu atoms are each square‐pyramidally coordinated by two N atoms of one phen ligand and three carboxyl O atoms of two maleato ligands with one carboxyl O atom at the apical position (d(Cu‐N) = 2.008, 2.012Å, equatorial d(Cu‐O) = 1.933, 1.969Å, axial d(Cu‐O) = 2.306Å). Two square‐pyramids are condensed via two apical carboxyl O atoms with a relatively larger Cu···Cu separation of 3.346(1)Å. The dinuclear complex molecules are assembled via the intermolecular π—π stacking interactions into 1D ribbons. Crossover of the resulting ribbons via interribbon π—π stacking interactions forms a 3D network with the tunnels occupied by H2O molecules. The title complex behaves paramagnetically between 5—300 K, following the Curie‐Weiss law χm(T—θ) = 0.435 cm3 · mol—1 · K with θ = 1.59 K. 相似文献
14.
The first selenite chloride hydrates, Co(HSeO3)Cl · 3 H2O and Cu(HSeO3)Cl · 2 H2O, have been prepared from solution and characterised by single‐crystal X‐ray diffraction. The cobalt phase adopts an unusual “one‐dimensional” structure built up from vertex‐sharing pyramidal [HSeO3]2–, and octahedral [CoO2(H2O)4]2– and [CoO2(H2O)2Cl2]4– units. Inter‐chain bonding is by way of hydrogen bonds or van der Waals' interactions. The atomic arrangement of the copper phase involves [HSeO3]2– pyramids and Jahn‐Teller distorted [CuCl2(H2O)4] and [CuO4Cl2]8– octahedra, sharing vertices by way of Cu–O–Se and Cu–Cl–Cu bonds. Crystal data: Co(HSeO3)Cl · 3 H2O, Mr = 276.40, triclinic, space group P 1 (No. 2), a = 7.1657(5) Å, b = 7.3714(5) Å, c = 7.7064(5) Å, α = 64.934(1)°, β = 68.894(1)°, γ = 71.795(1)°, V = 337.78(7) Å3, Z = 2, R(F) = 0.036, wR(F) = 0.049. Cu(HSeO3)Cl · 2 H2O, Mr = 263.00, orthorhombic, space group Pnma (No. 62), a = 9.1488(3) Å, b = 17.8351(7) Å, c = 7.2293(3) Å, V = 1179.6(2) Å3, Z = 8, R(F) = 0.021, wR(F) = 0.024. 相似文献
15.
Cyclohexane and piperidine ring reversal in 1-(3-pentyloxyphenylcarbamoyloxy)-2-dialkylaminocyclohexanes was investigated by 13C NMR. An unusually low conformational energy ΔG = 0.59 kJ mol?1 and activation parameters ΔG≠218 = 43.8 ± 0.4 kJ mol?1, ΔH≠ = 48.9 ± 2.5 kJ mol?1 and ΔS≠ = 23 ± 9 J mol?1 K?1 were found for the diequatorial to diaxial transition of the cyclohexane ring in the trans-pyrrolidinyl derivative. In the trans-piperidinyl derivative, ΔG222 = 44.7 ± 0.5 KJ mol?1, ΔH≠ = 55.7 ± 6.3 kJ mol?1 and ΔS≠ = 51 ± 21 J mol?1 K?1 was found for the piperidine ring reversal from the non-equivalence of the α-carbons. 相似文献
16.
《Journal of Inorganic and Nuclear Chemistry》1978,40(6):1095-1098
The volumes of activation for the acid hydrolysis of Co(C2O4)3−3 and Cr(C2O4)3−3 at 50°C and [H+] = 1.0 m (HClO4) are 10.8 ± 0.4 and −6.3 ± 0.4 cm3 mol−1, respectively. For the corresponding Rh(C2O4)3−3 reaction, measured at 60°C, ΔV≠exp = − 7.9 ± 0.6 cm3 mol−1. The remaining activation parameters were found to be 123±3, 87.8±2.5 and 82.7±2.1 kJ mol−1 for ΔH≠ and 84±9, −38±8 and 90±6J K−1 mol−1 for ΔS≠, respectively, at [H+] = μ = 1.0 M. 相似文献
17.
M. E. Gurskii P. A. Belyakov K. A. Lyssenko A. L. Semenova Yu. N. Bubnov 《Russian Chemical Bulletin》2014,63(2):480-486
2D 1H-1H EXSY NMR spectroscopy show that the free energy of activation ΔG ≠ in six 3-allyl-3-borabicyclo[3.3.1]nonane derivatives is significantly higher (72–86 kJ mol?1) than that in typical allylboranes (48–66 kJ mol?1). For the first member of the series, viz., 3-allyl-3-borabicyclo[3.3.1]nonane, the activation parameters of the permanent allylic rearrangement were also determined (ΔH ≠ = 82.7±3.4 kJ mol?1, ΔS ≠ = ?11.8±10.3 J mol?1 K?1, E A = 85.5±3.4 kJ mol?1, lnA = 29.2±1.2). 相似文献
18.
Radhey M. Naik Abhinav Agarwal Amit K. Verma Shiv Bali S. Yadav Basant Kumar 《国际化学动力学杂志》2009,41(4):215-226
The kinetics and mechanism of Hg2+‐catalyzed substitution of cyanide ion in an octahedral hexacyanoruthenate(II) complex by nitroso‐R‐salt have been studied spectrophotometrically at 525 nm (λmax of the purple‐red–colored complex). The reaction conditions were: temperature = 45.0 ± 0.1°C, pH = 7.00 ± 0.02, and ionic strength (I) = 0.1 M (KCl). The reaction exhibited a first‐order dependence on [nitroso‐R‐salt] and a variable order dependence on [Ru(CN)64?]. The initial rates were obtained from slopes of absorbance versus time plots. The rate of reaction was found to initially increase linearly with [nitroso‐R‐salt], and finally decrease at [nitroso‐R‐salt] = 3.50 × 10?4 M. The effects of variation of pH, ionic strength, concentration of catalyst, and temperature on the reaction rate were also studied and explained in detail. The values of k2 and activation parameters for catalyzed reaction were found to be 7.68 × 10?4 s?1 and Ea = 49.56 ± 0.091 kJ mol?1, ΔH≠ = 46.91 ± 0.036 kJ mol?1, ΔS≠ = ?234.13 ± 1.12 J K?1 mol?1, respectively. These activation parameters along with other experimental observations supported the solvent assisted interchange dissociative (Id) mechanism for the reaction. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 215–226, 2009 相似文献
19.
The self‐assembly of NiCl2·6H2O with a diaminodiamide ligand 4,8‐diazaundecanediamide (L‐2,3,2) gave a [Ni(C9H20N4O2)(Cl)(H2O)] Cl·2H2O ( 1 ). The structure of 1 was characterized by single‐crystal X‐ray diffraction analysis. Structural data for 1 indicate that the Ni(II) is coordinated to two tertiary N atoms, two O atoms, one water and one chloride in a distorted octahedral geometry. Crystal data for 1: orthorhombic, space group P 21nb, a = 9.5796(3) Å, b = 12.3463(4) Å, c = 14.6305(5) Å, Z = 4. Through NH···Cl–Ni (H···Cl 2.42 Å, N···Cl 3.24 Å, NH···Cl 158°) and OH···Cl–Ni contacts (H···Cl 2.36 Å, O···Cl 3.08 Å, OH···Cl 143°), each cationic moiety [Ni(C9H20N4O2) (Cl)(H2O)]+ in 1 is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chainlike structure. Thermogrametric analysis of compound 1 is consistent with the crystallographic observations. The electronic absorption spectrum of Ni(L‐2,3,2)2+ in aqueous solution shows four absorption bands, which are assigned to the 3A2g → 3T2g, 3T2g → 1Eg, 3T2g → 3T1g, and 3A2g → 3T1g transitions of triplet‐ground state, distorted octahedral nickel(II) complex. The cyclic volammetric measurement shows that Ni2+ is more easily reduced than Ni(L‐2,3,2)2+ in aqueous solution. 相似文献
20.
Reactions of a freshly prepared Zn(OH)2‐2x(CO3)x · yH2O precipitate, phenanthroline with azelaic and sebacic acid in CH3OH/H2O afforded [Zn(phen)(C9H15O4)2] ( 1 ) and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C9H15O4)2] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C9H15O4)2] complexes. Compound 2 is built up from crystal H2O molecules and the centrosymmetric binuclear [Zn2(phen)2(H2O)2(C10H16O4)2] complex, in which two [Zn(phen)(H2O)]2+ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H2O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)Å3, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)Å3, Z = 1. 相似文献