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1.
A series of dioxomolybdenum(VI) complexes with similar hydrazone ligands have been prepared, specifically [MoO2L1(MeOH)] (1), [MoO2L2(MeOH)] (2) and [MoO2L3(MeOH)] (3), where L1, L2 and L3 are the dianionic forms of 2-chloro-N′-(2-hydroxybenzylidene)benzohydrazide, 2-chloro-N′-(2-hydroxy-5-methylbenzylidene)benzohydrazide and N′-(3-bromo-5-chloro-2-hydroxybenzylidene)-2-chlorobenzohydrazide, respectively. The complexes were characterized by physicochemical and spectroscopic methods and also by single-crystal X-ray determination. The hydrazone ligands coordinate to the Mo atoms through their phenolate O, imine N and enolic O atoms. The Mo atoms are six-coordinated in octahedral geometries. The complexes show high catalytic activities and selectivities in the epoxidation of cyclohexene with tert-butylhydroperoxide as primary oxidant.  相似文献   

2.
Two new dioxomolybdenum(VI) complexes, [MoO2L1(MeOH)] (I) and [MoO2L2] (II), where L1 and L2 are the anionic forms of N'-(2-hydroxy-3,5-di-tert-butylbenzylidene)-4-methoxybenzohydrazide and 2-amino-N'-(2-hydroxy-3,5-di-tert-butylbenzylidene)benzohydrazide, respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination (CF files CCDC nos. 1448089 (I), 1487063 (II)). The crystal of I is monoclinic: space group P21/n, a = 7.353(1), b = 24.758(3), c = 13.891(2) Å, β = 101.013(2)°, V = 2482.3(6) Å3, Z = 4, R 1 = 0.0848, wR 2 = 0.2050. The crystal of II is monoclinic: space group P21/c, a = 6.752(1), b = 16.947(1), c = 19.510(1) Å, β = 96.891(2)°, V = 2216.5(4) Å3, Z = 4, R 1 = 0.0670, wR 2 = 0.1638. The Mo atom in complex I is in octahedral coordination, with three donor atoms of the hydrazone ligand, two oxo groups, and one methanol O atom. The Mo atom in complex II is in square pyramidal coordination, with three donor atoms of the hydrazone ligand, and two oxo groups. The complexes have interesting catalytic properties for sulfoxidation reactions.  相似文献   

3.
A pair of structurally similar dioxomolybdenum(VI) complexes with general formula [MoO2(L)(MeOH)] (L = L1 = N’-(3,5-dibromo-2-hydroxybenzylidene)-2-hydroxybenzohydrazide for I, L = L2 = N’-(3,5-dibromo-2-hydroxybenzylidene)-2-methylbenzohydrazide for II), have been prepared and characterized by elemental analysis, IR spectra, and single crystal X-ray determination (CIF files CCDC nos. 917823 (I) and 917824 (II)). The hydrazone ligands coordinate to the Mo atoms through phenolate oxygen, imine nitrogen, and enolic oxygen atoms. The Mo atom in each complex is six-coordinated in an octahedral geometry. The crystals of the complexes are stabilized by hydrogen bonds. The complexes and the ligands were assayed for antibacterial activities against three Gram-positive bacterial strains (B. subtilis, S. aureus, and S. faecalis) and three Gram-negative bacterial strains (E. coli, P. aeruginosa, and E. cloacae) by MTT method. As a result, the complexes showed effective antimicrobial activity against the microorganisms tested.  相似文献   

4.
Two Mo(VI) aroylhydrazone complexes, cis-[MoO2(L1)(CH3OH)] (I) and cis-[MoO2(L2)(CH3OH)] (II), derived from 2-bromo-N'-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (H2L1) and 2-bromo-N'-(2-hydroxy-4-methoxybenzylidene)benzohydrazide (H2L2), respectively, are reported. The complexes were characterized by elemental analyses, infrared and electronic spectroscopy, and single crystal structure analysis (CIF files CCDC nos. 1443679 (I) and 1443678 (II)). The Mo atoms are coordinated by two cis terminal oxygen, ONO from the aroylhydrazone ligand, and methanol oxygen. Complex I crystallized as monoclinic space group P21/c with unit cell dimensions a = 8.075(2), b = 13.905(1), c = 16.448(1) Å, β = 91.282(2)°, V = 1846.5(4) Å3, Z = 4, R 1 = 0.0859, wR 2 = 0.2066. Complex II crystallized as triclinic space group P \(\overline 1 \), with unit cell dimensions a = 8.0824(6), b = 10.5919(8), c = 10.7697(8), α = 96.432(2)°, β = 97.438(2)°, γ = 103.119(2)°, V = 880.8(1) Å3, Z = 2, R 1 = 0.0271, wR 2 = 0.0571. The complexes were tested as catalyst for the oxidation of olefins and showed effective activity.  相似文献   

5.
The preparation of Mo(VI) hydrazone complexes, cis-[MoO2L1(CH3OH)] (I) and cis-[MoO2L2(CH3OH)] (II), derived from N'-(3-bromo-2-hydroxybenzylidene)-2-chlorobenzohydrazide (H2L1) and N'-(3-bromo-2-hydroxybenzylidene)-4-bromobenzohydrazide (H2L2), respectively, is reported. The complexes were characterized by elemental analyses, infrared and electronic spectroscopy, and single crystal structure analysis (CIF files ССDС nos. 1426875 (I), 1426871 (II)). The Mo atoms are coordinated by two cis terminal oxygen, ONO from the hydrazone ligand, and methanol oxygen. Even though the hydrazone ligands and the coordination sphere in both complexes are similar, the unit cell dimensions and the space groups are different. Complex I crystallized as orthorhombic space group Pca21 with unit cell dimensions a = 27.887(2), b = 8.0137(7), c = 15.544(1) Å, V = 3473.8(5) Å3, Z = 8, R 1 = 0.0450, wR 2 = 0.0539. Complex II crystallized as triclinic space group P1, with unit cell dimensions a = 8.2124(4), b = 8.5807(5), c = 12.9845(8) Å, α = 83.366(2)°, β = 79.201(2)°, γ = 80.482(2)°, V = 883.03(9) Å3, Z = 2, R 1 = 0.0278, wR 2 = 0.0569. The complexes were tested as catalyst for the oxidation of olefins, and showed effective activity.  相似文献   

6.
Structural features of eight binuclear complexes with the general formula [{MoO2(L bi n )}2(μ-O)] (IVIII) (Lbi is a bidentate chelate ligand, n = 1–8), in which the coordination number of Mo atoms is five, are considered. The parameter τ = (A–B)/60, where A and B are the greatest bond angles among the ten bond angles at the Mo atoms in coordination pentahedra, can be used as a criterion characterizing the coordination polyhedron of the molybdenum atom in complexes IVIII. The parameter τ is zero for an ideal square pyramid and unity for an ideal trigonal bipyramid.  相似文献   

7.
Two methanol coordinated zinc(II) complexes, [Zn(L1)(MeOH)] (I) and [Zn(L2)(MeOH)] (II), where L1 and L2 are the dianionic form of N,N'-bis(5-fluorosalicylidene)ethane-1,2-diamine and N,N'-bis(5-fluorosalicylidene)propane-1,2-diamine, respectively, have been synthesized and characterized by physical chemical methods and single crystal X-ray diffraction (CIF files CCDC nos. 950907 (I) and 950908 (II)). Crystallographic data for I: triclinic, P \(\bar 1\), a = 8.8765(8), b = 9.6577(9), c = 10.5117(9) Å, α = 114.590(2)°, β = 91.648(3)°, γ = 97.114(3)°, V = 809.87(13) Å3, Z = 2, R 1 = 0.0307, wR 2 = 0.0698. Crystallographic data for II: orthorhombic, Pca21, a = 22.946(2), b = 7.6942(7), c = 9.6234(8) Å, V = 1699.0(2) Å3, Z = 4, R 1 = 0.0320, wR 2 = 0.0676. X-ray crystal structural study indicated that the coordination environment around each zinc(II) atom in the complexes is a five-coordinated distorted pyramid in which the apical position is occupied by a methanol oxygen atom, and the basal plane is defined by the nitrogen and oxygen donor atoms of the Schiff base ligand. The antibacterial activities of the complexes were assayed.  相似文献   

8.
Six new homobimetallic bis-diorganotin(IV) complexes: [Me2Sn]2L (1), [Et2Sn]2L (2), [n-Bu2Sn]2L (3), [Ph2Sn]2L (4), [Oct2Sn]2L (5) and [n-BuClSn]2L (6) (H 4 L=N1′, N6′-bis(2-hydroxybenzylidene)adipodihydrazide) have been synthesized and structurally characterized by means of elemental analysis, mass spectroscopy, FT-IR, NMR (1H, 13C{1H}, 119Sn) and single-crystal X-ray diffraction. Spectroscopic studies indicate coordination of the ligand to the diorganotin(IV) moieties via iminolic oxygen, nitrogen and phenolic oxygen atoms generating pentacoordinated tin centers. Single-crystal X-ray analysis of (1) revealed homobimetallic nature of complex with dimethyltin moieties oriented in trans-conformation. The ligand is non-planar with each Sn atom in a distorted square pyramidal coordination geometry. Packing diagrams suggest the essential role of C–HN and C–HO interactions in generating supramolecular assembly. The ligand and complexes were screened for in vitro antimicrobial activity and cytotoxicity. Compound (4) exhibits highest cytotoxicity.  相似文献   

9.
Synthesis of some new oxomolybdenum(V) and dioxomolybdenum(VI) complexes with a Schiff base isonicotinioyl(5-bromo-2-hydroxybenzylidene)hydrazide (L) derived from 5-bromosalicylaldehyde and isonicotinoylhydrazide are reported. The complexes have been characterized by elemental analyses, molar conductance, magnetic susceptibility data, IR, UV-Vis, EPR, 1H NMR, and FAB mass spectral studies. The physicochemical studies and spectral data indicate that L acts as a monovalent tridentate chelating agent. The FAB mass and X-band EPR spectra indicate that the pentavalent Mo in the complex is monomeric in nature. The X-ray diffraction studies of the complex [MoO(L)Cl2] (I) correspond to the orthorhombic crystal lattice with the unit cell dimensions a = 16.11, b = 12.20, and c = 7.5 Å. The electrochemical behavior of the complex was investigated by cyclic voltammetry. All the complexes are found to be neutral with the distorted octahedral geometry. The thermal properties of the complex I were investigated by thermogravimetric techniques. The ligand L and the complexes I and [MoO2(L)Cl] (II) were screened for their in vitro antimicrobial activity. The complexes exhibited higher activity than L. The 3D molecular modeling and analysis for bond length and bond angles have also been carried out for complex I.  相似文献   

10.
Two new oxovanadium(V) complexes, [VOL1(OCH3)(CH3OH)] (I) and [VOL2(OCH3)] (II), where L1 and L2 are the di-anionic form of N'-[1-(5-fluoro-2-hydroxyphenyl)methylidene]nicotinohydrazide and N'-(5-fluoro-2-hydroxybenzylidene)-2-hydroxynaphthylhydrazide, respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination (CIF files CCDC nos. 891852 (I), 891853 (II)). The crystal of I is monoclinic: space group P21/c, a = 8.061(1), b = 15.293(2), c = 13.471(2) Å, ß = 92.595(2)°, V = 1658.8(4) Å3, Z = 4. The crystal of II is monoclinic: space group P21/n, a = 7.4454(9), b = 8.0833(9), c = 28.906(2) Å, ß = 92.644(2)°, V = 1737.8(3) Å3, Z = 4. The V atom in I is in an octahedral coordination, and that in II is in a square-pyramidal coordination. The antibacterial activity of the compounds against various bacteria was assayed.  相似文献   

11.
This paper describes the hydrothermal synthesis, full characterization, and architectural diversity of three intriguingly bioactive cobalt–organic frameworks, namely, 3D [Co(HL ? )2(BPY)] n ·4nH2O (1), 2D [Co(HL ? )2(BPE)] n (2), and 2D [Co(HL ? )2(DPP)] n (3) coordination polymers, synthesized through a mixed ligand strategy using H 2 L (1-H-indazole-3-carboxylic acid) as a main structural block and the flexible bipyridine and its derivatives (BPY = 4,4′-bipydine, BPE = 1,2-bis(4-pyridyl)ethane, DPP = 1,3-bis(4-pyridyl)propane) as auxiliary ligand sources. Complexes 13 were isolated as air stable and slightly soluble crystalline solids and characterized using elemental analysis, FT-IR, electrochemical technique, thermogravimetric analysis, powder X-ray diffractometer, and single-crystal X-ray crystallography. The bipyridine derivatives played key roles in defining the structural space group and dimensionality feature of the obtained networks. The abundant H-bonding and ππ stacking interactions in complexes 13 gave rise to their intricate metal–organic structures of 3D (1), 2D (2), and 2D (3). In addition, the solutions of complexes 13 showed profound antifungal activities against the selected strain of Colletotrichum musae compared with the controlled group using benomyl as a traditional agrochemical fungicide.  相似文献   

12.
Three coordination polymers based on the new ligand oxamide N,N-bis(4-phthalic acid), namely [Zn(L)0.5-(2,2′-bpy)] n (1), [Ni2(2,2′-bpy)4(µ 2-Ox)]L·3H2O (2) and [Cd(L)(1,10-phen)] (3) [L = oxamide N,N-bis(4-phthalic acid)], (2,2′-bpy = 2,2′-bipyridine), (1,10-phen = 1,10-phenanthroline), have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction: compound 1 is one-dimensional ladder-like coordination polymer, compound 2 exhibits a three-dimensional structure resulting in extensive hydrogen bonds built with the help of lattice water molecules, compound 3 also exhibits a three-dimensional supramolecular structure. All compounds were also characterized by elemental analysis, IR spectra and thermogravimetric analysis; furthermore, the magnetic measurements for 2 reveal antiferromagnetic coupling between the nickel(II) ions.  相似文献   

13.
The reaction of different macrocyclic metallic tectons and dicarboxylic acid ligand yielded six new coordination polymers, namely, {[(NiL1)(4,4'-Bpdc)] ? DMF ? 2.5H2O} n (I), {[(NiL2)(4,4'-Bpdc)] ? DMF ? 2.5H2O} n (II), [(NiL3)2(4,4'-Bpdc)1.5][(NiL3)(4,4'-Bpdc)] ? ClO4 ? 28H2O (III), {[(NiL4)(4,4'-Bpdc)] ? 4H2O} n (IV), {[(NiL5)(4,4'-Tpdc)] ? 5H2O} n (V), {[(NiL3)(4,4'-Tpdc)]} n (VI) (L1 = 1,4,7,9,12,14-hexaaza-tricyclo[12.2.1.14.7]octadecane, L2 = 1,3,10,12,15,18-hexaazatetracyclo[16.2.1.112.15.04.9]docosane, L3 = 11-methyl-1,4,8,10,13,15-hexaaza-tricyclo[13.3.1.14.8]icosane, L4 = 1,3,10,12,16,19-hexaazate-tracyclo[17.3.1.1.12.16,04.9]tetracosane, L5 = 1,4,8,10,13,15-hexaaza-tricyclo[13.3.1.14.8]icosane, 4,4'-Bpdc = 4,4'-biphenyldicarboxylic acid and 4,4'-Tpdc = 4,4'-terphenyldicarboxylic acid) (CIF files CCDC nos. 1055545–1055550 for I–VI, respectively). Except for the different conformations of the macrocyclic metallic tectons or dicarboxylic acid ligands, complexes I–VI crystallized under the same environment, however, they exhibit diverse packing mode of infinite 1D coordination polymers, showing macrocyle or dicarboxylic acid ligand regulated self-assemble. The solid states UV-Vis for complexes I–VI also have been investigated.  相似文献   

14.
Two new mononuclear Schiff base zinc(II) complexes, [ZnCl2(L1)] ? MeOH (I) and [Zn(L2)2] (II) (L1 = 2-bromo-4-chloro-6-[(2-ethylammonioethylimino)methyl]phenolate; L2 = 2-bromo-4-chloro-6-(isopropyliminomethyl)phenolate), have been prepared and characterized by elemental analyses, infrared and UV-Vis spectroscopy, and single-cyrstal X-ray diffraction (CIF files CCDC nos. 1408962 (I), 1408961 (II)). Complex I crystallizes in the triclinic space group \(P\overline 1\) with unit cell dimensions a = 9.859(1), b = 13.015(2), c = 19.817(3) Å, α = 73.591(2)°, β = 76.032(2)°, γ = 82.966(2)°, V = 2363.0(5) Å3, Z = 4, R 1 = 0.0925, and wR 2 = 0.2257. Complex II crystallizes in the monoclinic space group P21/c with unit cell dimensions a = 7.6387(7), b = 22.307(2), c = 21.443(2) Å, β = 96.216(3)°, V = 3632.4(6) Å3, Z = 8, R 1 = 0.0651, and wR 2 = 0.1100. The both Zn atoms in I is four-coordinated in a tetrahedral geometry by the NO donor set of the Schiff base ligand, and two Cl ligands. The Zn atom in II is in a tetrahedral geometry by two N and two O atoms from two Schiff base ligands. Crystals of the complexes are stabilized by hydrogen bonds and weak π…π interactions. Fluorescence property of the complexes have been determined.  相似文献   

15.
Two cis-dioxomolybdenum(VI) complexes [MoO2L] (L: L 1, 2 and L: L 2, 3) in a phenol-based sterically encumbered N2O2 ligand environment have been synthesized, and their crystallographic characterizations are reported. The orange crystals of 2 are monoclinic, space group P21/a with unit cell dimensions as a=16.2407(17) Å, b=7.2857(8) Å, c=18.400(2) Å, β=98.002(9)°, Z=4, and d cal=1.486 g cm?3. The light orange crystals of 3, however, are orthorhombic, space group, Pbcn, with unit cell dimensions a=8.3110(12) Å, b=12.637(3) Å, c=34.673(5) Å, Z=4, and d cal=1.187 g cm?3. The structures were refined by a full-matrix least-squares procedure on F 2 to a final R=0.046 (0.055 for 3) using 4944 (3677) all independent data. In both the cases, the Mo atom exists in a distorted octahedral geometry defined by a N2O4 donor set, which features a cis-Mo(–O)2 and a trans-Mo(OPh)2 arrangement. Compound 2 undergoes a quasireversible one-electron reduction at ?1.3 V vs Ag/AgCl reference due to MoVIO2/MoVO2 electron transfer and thus providing a rare example of steric solution to the comproportionation–dimerization problem encountered frequently in the development of valid biomimetic models for the active sites of oxomolybdenum enzymes.  相似文献   

16.
A new cobalt(II,III) complex, [CoIIIL2]2[Co 2 II (HL)2(OH2)2(CH3OH)2] ? 2H2O (I) and a new iron(III) complex, [FeIII(HL)2](NO3) (II), where L2– and HL are the dianionic and monoanionic form of N'-(2-hydroxybenzylidene)-3-methylbenzohydrazide, respectively, have been prepared and characterized by elemental analyses, infrared and UV-Vis spectroscopy and single-cyrstal X-ray diffraction (CIF files CCDC nos. 1417971 (I), 1417979 (II)). Complex I crystallizes in the monoclinic space group P21/n with unit cell dimensions a = 16.1665(9), b = 14.5692(8), c = 19.086(1) Å, β = 96.347(1)°, V = 4467.9(4) Å3, Z = 2, R 1 = 0.0521, and wR 2 = 0.1411. Complex II crystallizes in the orthorhombic space group Pbcn with unit cell dimensions a = 12.475(1), b = 12.202(1), c = 18.859(2) Å, V = 2870.8(4) Å3, Z = 4, R 1 = 0.0796, and wR 2 = 0.1981. The metal atoms in the complexes are in octahedral coordination. Crystals of the complexes are stabilized by hydrogen bonds. The efficiency of the aroylhydrazone and the two complexes was evaluated against B. subtilis, S. aureus, E. coli, P. fluorescence, C. albicans and A. niger, with the complexes demonstrating enhanced activity relatively to the free ligand.  相似文献   

17.
An end-to-end azido-bridged dinuclear copper(II) complex [Cu2L21,3-N3)](NO3) (I) and a mononuclear zinc(II) complex [ZnCl2(HL)] ? CH3OH (II), where L is 2-brom-4-chloro-6-[(2-morpholin- 4-ylethylimino)methyl]phenolate, have been prepared and characterized by elemental analyses, IR, and single crystal X-ray crystallographic determination (CIF files CCDC nos. 1415217 (I), 1415218 for (II)). The crystal of I is monoclinic: space group C2/c, a = 28.684(2), b = 7.1787(5), c = 18.292(1) Å, β = 117.887(3)°, V = 3329.1(4) Å3, Z = 4. The crystal of II is monoclinic: space group P21/c, a = 10.8207(9), b = 12.3398(7), c = 14.9477(7) Å, β = 93.473(3)°, V = 1992.2(2) Å3, Z = 4. The Schiff base ligand in I coordinates to the Cu atom through the phenolate O, imine N, and morpholine N atoms, while the Schiff base ligand in II coordinates to the Zn atom through the phenolate O and imine N atoms, with the morpholine N atom protonated. The effect of these complexes on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans was studied.  相似文献   

18.
Two new oxidovanadium(V) complexes, [VO(L)(Ehp)] (I) and [VO(L)(Aha)] (II), where L is the dianionic form of 4-bromo-N'-(4-oxopentan-2-ylidene)benzohydrazide (H2L), Ehp is the monoanionic form of 2-ethyl-3-hydroxy-4H-pyran-4-one (HEhp), and Aha is the monoanionic form of acetohydroxamic acid (HAha), were prepared and characterized by elemental analysis, infrared and electronic spectra, and 1H NMR spectra. Structures of the complexes were further confirmed by single crystal X-ray diffraction (CIF files CCDC nos. 1477847 (I), 1477850 (II)). H2L coordinates to the V atom through the two enolic O atoms and the imino N atom. The ligands Ehp and Aha coordinate to the V atoms through bidentate OO donor set. The V atoms of the complexes are in octahedral coordination, with the oxo group furnished the octahedral geometry. The complexes show effective antibacterial activity against Bacillus subtilis.  相似文献   

19.
Two new oxidovanadium(V) complexes, [VO(L1)(L)] (I) and [VO(L2)(L)] (II), where L1 and L2 are the dianionic form of N'-(2-hydroxy-5-methoxybenzylidene)pivalohydrazide (H2L1) and N'-(2-hydroxy-3-methoxybenzylidene)pivalohydrazide (H2L2), respectively, and L is the monoanionic form of 8-hydroxyquinoline (HL), were prepared and characterized by elemental analysis, infrared and electronic spectra, and 1H NMR spectra. Structures of the complexes were further confirmed by single crystal X-ray determination (CIF files CCDC nos. 1477854 (I), 1477856 (II)). H2L1 and H2L2 coordinate to the V atoms through the phenolate O, imino N, and enolate O atoms. 8-Hydroxyquinoline coordinates to the V atoms through bidentate ON donor set. The V atoms of the complexes are in octahedral coordination with the oxo group furnished the octahedral geometry. The complexes show effective antibacterial activity against Bacillus subtilis.  相似文献   

20.
Two crystalline host-guest complexes are synthesized and studied using X-ray diffraction analysis: (18-crown-6)sodium tribromide [Na(18-crown-6)]+ · Br 3 ? (I) and (18-crown-6)potassium tribromide (with an admixture of bromodiiodide) [K(18-crown-6)]+ · (Br0.25I2.75)? (II). The structures of compound I (space group P21/n, a = 8.957 Å, b = 8.288 Å, c = 14.054 Å, β = 104.80°, Z = 2) and compound II (space group Cc, a = 8.417 Å, b = 15.147 Å, c = 17.445 Å, β = 99.01°, Z = 4) are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.098 (I) and 0.036 (II) for all 2311 (I) and 2678 (II) independent measured reflections on a CAD-4 automated diffractometer (λMoK α). Similar crystalline complexes I and II exist as infinite chains of alternating complex cations and trihalide anions linked to each other through weak Na-Br or K-I coordination bonds. In [Na(18-crown-6)]+ and [K(18-crown-6)]+ complex cations, the Na+ or K+ cation (coordination number is eight) is located in the center of the cavity of the 18-crown-6 ligand and coordinated by the six O atoms and two terminal Br or I atoms of two trihalide anions lying on opposite sides of the rms plane of the crown ligand.  相似文献   

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