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1.
Coordination-chemistry of cis-Trioxotungsten(VI) Complexes. Crystal Structures of LWO 3 · 3 H 2O, [L′WO 2(OH)]Br, [LWO 2Br]Br, [L 2W 2O 5](S 2O 6) · 4 H 2O and [LWO 2(μ-O)WO(O 2) 2(OH 2)] (L = 1,4,7-Triazacyclonane; L′ = 1,4,7-Trimethyl-1,4,7-triazacyclononane) The cyclic triamines 1,4,7-triazacyclononane (L; C 6H 15N 3) and 1,4,7-trimethyl-1,4,7-triazacyclononane (L′; C 9H 21N 3) react in aqueous solution with WO 3 affording LWO 3 · 3 H 2O, 1 , and L′WO 3 · 3 H 2O, respectively, which yield [L′WO 2(OH)]Br, 2 , and [LWO 2Br]Br, 3 , in concentrated HBr solutions. In aqueous CH 3SO 3H solution 1 dimerizes. The iodide and dithionate 4 salts of [L 2W 2O 5] 2+ have been isolated. In 35% H 2O 2 complex 1 yields the neutral species [LWO 2(μ-O)WO(O 2) 2(H 2O)] 5 . The crystal structures of 1 – 5 have been determined by X-ray analysis. Crystal data: 1 : P2 1/c; a = 7.729(2), b = 14.887(3), c = 10.774(2) Å, β = 90.77(2)°, Z = 4; 2 : Cc; 8.910(3), b = 12.220(6), c = 13.279(6) Å, β = 101.31(3)°, Z = 4; 3 : Cmc2 1, a = 8.857(5), b = 12.062(7), c = 11.218(7) Å, Z = 4; 4 : Cc, a = 17.601(7), b = 12.906(7), c = 14.107(8) Å, β = 124.08(4)°, Z = 4; 5 : P2 12 12 1; a = 8.452(4), b = 11.301(6), c = 13.750(6) Å, Z = 4. 相似文献
2.
New tetranuclear compounds have been obtained by reacting binuclear complexes, [Zn 2L n (μ-OH)(H 2O) 2](ClO 4) 2, with sodium dicyanamide (HL n are end-off bicompartmental ligands resulting from condensation between 2,6-diformyl- p-cresol with N, N-dimethyl-ethylenediamine or 2-aminomethyl-pyridine). The complexes, [{L 1(μ-OH)Zn 2}( μ 1,5-dca) 2{Zn 2(μ-OH)L 1}](ClO 4) 2 ( 1) and [{Zn 2L 2( μ 3-OH)(dca)} 2](ClO 4) 2?·?2H 2O ( 2), have been characterized by single-crystal X-ray diffraction. The angular nature of the bridging dicyanamido induces the “M” shape of the tetranuclear cationic unit in 1. The tetranuclear cation, because of its particular shape, acts as a receptor toward one perchlorate ion, which is hydrogen bonded to the hydroxo groups. This tetranuclear unit in 2 has a defective heterocubane structure. The luminescence properties of the new tetranuclear complexes have been investigated. 相似文献
3.
New Co(II), Ni(II), and Cu(II) complexes with 4-(3-hydroxyphenyl)-1,2,4-triazole (L) with the compositions [Co 3L 6(H 2O) 5(C 2H 5OH)](NO 3) 6 · 2H 2O · C 2H 5OH ( I), [Ni 3L 6(H 2O) 6](NO 3) 6 · 2H 2O ( II), and [M 3L 6(H 2O) 6](ClO 4) 6 · nH 2O (M = Co2 +, n = 2 ( III); Ni 2+, n = 2 ( IV); Cu 2+, n = 0 ( V)) are synthesized. The complexes are studied by X-ray structure analysis, X-ray diffraction analysis, UV and IR spectroscopy,
and the statistical magnetic susceptibility method. All compounds have the linear trinuclear structure. Ligand L is coordinated
to the metal ions by the N(1) and N(2) atoms of the heterocycle according to the bidentate bridging mode. In all compounds
the coordination polyhedron of the metal atom is a distorted octahedron. The molecular and crystal structures of compound
I, [Co 3L 6(H 2O) 6](ClO 4) 6 · 8C 2H 5OH ( IIIa), and [Ni 3L 6(H 2O) 6](ClO 4) 6 · 8C 2H 5OH ( IVa) are determined. 相似文献
4.
The preparation and the properties of 7 salts containing the complex cation [Co 2{NO 2, OH}(NH 3) 8] 4+ are described. Furthermore, a di-μ-hydroxo complex of the composition [Co 2{OH} 2NO 2(NH 3) 7](ClO 4) 3 · H 2O has been prepared. 相似文献
5.
The pendant‐armed ligands L 1 and L 2 were synthesized by N‐alkylation of the four secondary amine groups of the macrocyclic precursor L using o‐nitrobenzylbromide (L 1) and p‐nitrobenzylbromide (L 2). Nitrates and perchlorates of Cu II, Ni II and Co II were used to synthesize the metal complexes of both ligands and the complexes were characterized by microanalysis, MS‐FAB, conductivity measurements, IR and UV‐Vis spectroscopy and magnetic studies. The crystal structures of L 1, [CuL 1](ClO 4) 2·CH 3CN·H 2O, [CuL 2](ClO 4) 2·6CH 3CN, [CuL 2][Cu(NO 3) 4]·5CH 3CN·0.5CH 3OH and [NiL 2](ClO 4) 2·3CH 3CN·H 2O were determined by single crystal X‐ray crystallography. These structural analysis reveal the free ligand L 1, three mononuclear endomacrocyclic complexes {[CuL 1](ClO 4) 2·CH 3CN·H 2O, [CuL 2](ClO 4) 2·6CH 3CN and [NiL 2](ClO 4) 2·3CH 3CN·H 2O} and one binuclear complex {[CuL 2][Cu(NO 3) 4]·5CH 3CN·0.5CH 3OH} in which one of the metals is in the macrocyclic framework and the other metal is outside the ligand cavity and coordinated to four nitrate ions. 相似文献
6.
Polynuclear Cobalt Complexes. V. Preparation of tetrakis (ethylenediamine)-μ-peroxo-μ-amido and μ-peroxo-μ-thiocyanato-dicobalt (III) complexes starting from tetrakis (ethylenediamine)bis-(ammine)-μ-peroxo-dicobalt (III)-tetraperchlorate Racemic tetrakis (ethylenediamine)-μ-peroxo-μ-amido-dicobalt (III) thiocyanate and its corresponding hydroperoxo- and superoxo-complexes have been isolated from [(en) 2(NH 3)Co(O 2)(NH 3)(en) 2](ClO 4) 4. A new binuclear peroxo complex containing thiocyanate as bridging ligand was prepared by the same method. The stretching frequencies of the CN- and CS-group as well as the NCS-bending frequence in the IR. spectrum of [(en) 2Co(O 2, SCN)Co(en) 2](NO 3) 3 suggest that the μ-thiocyanato group is N-bonded (2050, 750, 475 cm ?1). A comparison of IR. spectra of known singly and doubly bridged μ-peroxo complexes is made. Characteristic absorption bands, assignable to ν(O? O) and ν(Co? O) are given. 相似文献
7.
Two new complexes of the Ln 2(oda) 3· nH 2O (oda =–O 2CCH 2OCH 2CO 2–) series are reported, i.e. {[Pr 2(C 4H 4O 5) 3(H 2O) 3]·5H 2O} n and {[Nd 2(C 4H 4O 5) 3(H 2O) 6]·C 4H 6O 5·‐2H 2O} n. The former is isostructural with the reported La analogue, while the latter is a new structural variety within the series. Each compound exhibits two independent nine‐coordinated Ln centres showing a variety of coordination geometries. 相似文献
8.
Complexes of Chromium Containing 1,5,9-Triazacyclododecane: Synthesis, Magnetism, and Crystal Structure of Tri-μ-hydroxo-bis[(1,5,9-triazacyclododecane) chromium (III)] tribromide · Dihydrate; Kinetic and Mechanism of its Bridge-cleavage with Hydroxide The oxidative decarbonylation of LCr(CO) 3 (L = 1,5,9-triazacyclododecane) with bromine yields green LCrBr 3. Base hydrolysis affords red [LCr(μ-OH) 3CrL] 3+, whereas in the presence of acetate ions [L 2Cr 2(μ-OH) 2(CH 3CO 2)] 3+ is formed. [LCr(μ-OH) 3CrL]Br 3· 2 H 2O crystallizes in the orthorhombic space group P2 12 12 1 with 8 formula units per unit cell. Two Cr III centers are connected via three OH ? bridges; the spins of d 3-electronic configuration are coupled intramolecularly, antiferromagnetically (2J = ?96 cm ?1). With excess OH ? but not with protons the tri-μ-hydroxo species is cleaved to give [L 2Cr 2(OH) 2(μ-OH) 2] 2+. The kinetics of this reaction have been measured using the stopped flow technique. The mechanism is discussed. 相似文献
9.
Three polynuclear clusters, [Cu 4L 8](ClO 4) 4·4H 2O ( 1), [Zn 3L 6(H 2O) 6](ClO 4) 6·6H 2O ( 2), and [Mn 3L 6(CH 3OH) 6](ClO 4) 6·4.5H 2O ( 3) (L?=?4-(4-hydroxyphenyl)-1,2,4-triazole), obtained by the reactions of M(ClO 4) 2·6H 2O with L have been isolated and structurally characterized. Complex 1 featured a tetranuclear Cu(I) structure. Both 2 and 3 are linear hexapositive trimers linked by three N1,N2–1,2,4-triazole ligands to the divalent central and terminal metal ions. Furthermore, the luminescence properties of 2 were investigated at room temperature in the solid state. 相似文献
10.
Crystal and Molecular Structure of μ-5-Pyrimidinecarboxylato(O,O′)-di-μ-hydroxo-bis-[triamminecobalt(III)]perchlorate μ-5-Pyrimidinecarboxylato(O,O′)-di-[μ-hydroxo-bis(triamminecobalt)(III)]perchlorate, [(NH 3) 3Co-μ(OH, OH, C 5H 4N 2O 2)Co(NH 3) 3](ClO 4) 4, crystallizes in the orthorhombic space group Ibca with a = 12.686, b = 13.079, c = 31.785 Å and Z = 8 formula units. The complex cation adopts C 2 symmetry, but no mirror plane is present. The Co? Co separation in the binuclear complex is 2.794 Å. The four-membered ring defined by the two Co atoms and the bridging oxygens is folded along the O? O axis, the interplanar angle being 154°. One of the ClO 4 tetrahedra is disordered over two sites in the crystal. 相似文献
11.
The pyridine‐2‐carbaldehyde semicarbazone ligand (HL) reacts with iron(II) and copper(II) perchlorates in boiling ethanol to yield red‐violet [Fe II(HL) 2](ClO 4) 2·H 2O ( 1 ) and light‐green crystals [Cu II(HL) 2](ClO 4) 2·H 2O ( 2 ). The crystals are triclinic with the metal ions in an octahedral environment, coordinated to two nitrogen and one oxygen‐donor atom from HL. Electronic, magnetic and electrochemical properties are presented as well. 相似文献
12.
Novel oligonuclear complexes of Co(II), Ni(II), and Cu(II) with 4-(3,4-dichlorophenyl)-1,2,4-triazole (L) of the composition [M 3L 10(H 2O) 2](NO 3) 6 (M = Co(II), Ni(II)), [Ni 3L 6(H 2O) 6]Hal 6 (Hal = Cl ?, Br ?), and [Cu 5L 16(H 2O) 2](NO 3) 10 · 2H 2O were synthesized and studied by magnetic susceptibility, electronic and IR spectroscopy, and powder X-ray diffraction methods. All the above complexes are X-ray amorphous. Antifer-romagnetic exchange interactions between the M 2+ ions were discovered in the [Co 3L 10(H 2O) 2](NO 3) 6 and [Ni 3L 10(H 2O) 2](NO 3) 6 complexes, whereas ferromagnetic exchange interactions were observed in the complexes [Ni 3L 6(H 2O) 6]Cl 6, [Ni 3L 6(H 2O) 6]Br 6, and [Cu 5L 16(H 2O) 2](NO 3) 10 · 2H 2O. 相似文献
13.
(1,4,7‐Trithiacyclononane)silver trifluoromethanesulfonate crystallizes in a tetrameric form from nitromethane, to give the title compound, [Ag 4(C 6H 12S 3) 4](CF 3SO 3) 4·2CH 3NO 2. The complex cation consists of four [Ag L] + units ( L is 1,4,7‐trithiacyclononane), with four Ag—S—Ag bridges forming a cyclic tetramer. The almost planar Ag 4S 4 ring takes an octagonal form. 相似文献
14.
Crown Thioether Complexes of Lead (II), Zinc(II), and Cadmium (II). Crystal Structures of [PbL 2(ClO 4) 2] and [ZnL 2](ClO 4) 2 · CH 3CN (L = 1,4,7 - Trithiacyclononane) The reaction of 1,4,7-trithiacyclononane (L) with the perchlorate salts of lead(II) and zinc(II) in CH 3CN (2:1) affords colorless crystals of [PbL 2(ClO 4) 2] and [ZnL 2](ClO 4) 2 · CH 3CN, respectively, The crystal structures have been determined. The Pb II centre is coordinated to six sulfur atoms (the average distance Pb? S is 3.076 Å) and two oxygen atoms, one of each ClO 4? anion (monodentate ClO 4?). A distorted square antiprismatic polyhedron is thus generated. In [ZnL 2](ClO 4) 2 · CH 3CN the zinc(II) centre is octahedrally surrounded by six sulphur atoms (average distance Zn? S = 2.494 Å); the ClO 4? anions are not coordinated. For[CdL 2](ClO 4) 2 · H 2O an analogous structure is proposed. 相似文献
15.
Two pyrazole-based polydentate ligands, 1,3- bis(5-methyl-3-phenylpyrazol-1-yl)-propan-2-ol (Hmppzpo) and 1,3- bis(5-methyl-3- p-isopropylphenylpyrazol-1-yl)-propan-2-ol (Hmcpzpo), have been synthesized. A third ligand, 1,3- bis(3,5-dimethylpyrazol-1-yl)-propan-2-ol (Hdmpzpo), has been synthetically modified. Seven new M(II) coordination compounds of general formula M 2L 2X 2 (M?=?Zn, Ni; X?=?NO 3 or ClO 4; L?=?dmpzpo, mppzpo or mcpzpo) or MLX (M?=?Pd; L?=?dmpzpo; X?=?Cl) were synthesized and structurally characterized by elemental analysis and FT-IR analysis. The crystal structures of [Zn 2(μ-dmpzpo-O,N,N′) 2(NO 3) 2]?·?2H 2O ( 1?·?2H 2O), [Ni 2(μ-dmpzpo-O,N,N′) 2(CH 3CN) 2](ClO 4) 2 ( 2) and Pd(μ-dmpzpo-N,N′)Cl 2 ( 4) were determined by single-crystal X-ray crystallography. The crystal structures show that complexes 1?·?2H 2O and 2 are center-symmetric dinuclear compounds, with two metal ions bridged by two alkoxo groups and each metal ion with a distorted square-pyramidal environment. The palladium complex, 4, displayed square-planar coordination geometry around the Pd(II) ion with trans arrangement. 相似文献
16.
New complexes of Co(II), Ni(II), and Cu(II) nitrates, chlorides, and perchlorates with 4-(4-hydroxyphenyl)-1,2,4-triazole (L) were obtained and examined by single-crystal X-ray diffraction, X-ray powder diffraction, and electronic absorption and IR spectroscopy. The cations of all the complexes have linear trinuclear structures. Ligand L is coordinated to the metal ions in a bidentate bridging fashion through the N(1) and N(2) atoms of the heterocycle. The coordination polyhedron of the metal atoms is a distorted octahedron. The molecular and crystal structures of the complexes [Co 3L 6(H 2O) 6](ClO 4) 6 · 3C 2H 5OH · 3.75H 2O and [M 3L 6(H 2O) 6](ClO 4) 6 · 6H 2O (M = Cu 2+ and Ni 2+) were determined. 相似文献
17.
Sandwich coordination complexes, [Ln III(H 3L) 2]X 3? solvents, of Tb(III), Eu(III), Dy(III), Ho(III) and Er(III) were prepared with two new zwitterionic ester-substituted tripodal amine ligands, tris((2-hydroxy-5- n-butyl benzoate)aminoethyl)-amine (H 3L1) and tris((2-hydroxy-5-methyl benzoate)aminoethyl)-amine (H 3L2). These ligands were synthesised by condensation of the appropriately substituted salicylaldehyde with tris(2-aminoethyl)amine (tren) followed by in situ reduction of the tris-imine to tris-amine. Subsequent 2:1 reaction with lanthanide(III) ions yields [Ln III(H 3L) 2]X 3? solvents ( L = L1, L2; X = Cl ?, NO 3?; solvents = MeOH or H 2O). All complexes were characterised by microanalysis, infrared spectroscopy, high resolution mass spectrometry and solid-state photoluminescence measurements. The crystal structures of [Tb III(H 3L1) 2]Cl 3·6MeOH, [Dy(H 3L1) 2]Cl 3·6MeOH, [Eu III(H 3L1) 2]Cl 3·6MeOH and [Tb III(H 3L1) 2](NO 3) 3 reveal high-crystallographic ?3 symmetry at the O 6-coordinated octahedral lanthanide(III) ions and that the tripodal ligands are bound in zwitterionic form: the protons from the phenolic oxygens have migrated to the amino nitrogens. Photoluminescence measurements indicate various degrees of energy transfer of the ligand chromophore to the lanthanide ions, as both ligand and lanthanide emission features are observed. Despite the high-crystallographic symmetry and the likely small transverse magnetic anisotropy of the complexes, no evidence of slow relaxation of the magnetisation, characteristic of a single-molecule magnet, was observed for [Tb III(H 3L1) 2]Cl 3·MeOH·3H 2O, [Dy III(H 3L1) 2]Cl 3·6H 2O, [Ho III(H 3L1) 2](NO 3) 3·2H 2O, [Er III(H 3L1) 2]·H 2O and [Tb III(H 3L1) 2](NO 3) 3 down to 2.0 K. 相似文献
18.
Three new cobalt complexes were synthesized by solid-state reaction at room temperature and the resultant Co complexes reacted
with two equivalent oxygen molecules at room temperature to produce the oxygenated complexes [Co·(L 1) 2·(O 2) 2](NO 3) 2·2H 2O (L 1 = N, N’-bis(4-hydroxyl-3-methoxy-benzyl)-diethylenetriamine), [Co·(L 2) 2·(O 2) 2](NO 3) 2·2H 2O (L 2 = N, N’-bis(4-hydroxyl-3-methoxy-benzyl)-triethylenetetramine), and [Co·(L 3) 2·(O 2) 2](NO 3) 2·2H 2O (L 3 = N, N’-bis(4-hydroxyl-3-methoxy-benzyl-tetraethylenepentamine). The oxygenated complexes were characterized by elemental
analysis, IR (Infrared), 1H-NMR (Nuclear Magnetic Resonance), and UV-Vis (Ultraviolet Visual) spectrometry, and TG/DTA (Thermogravimetry/Differential
Thermal Analysis) analysis, and molar conductance. The coordinated oxygen contents in the oxygenated complexes were also determined
by weight method. It was supposed that only one O 2 molecule coordinated to the Co ion forming a superoxo type oxygenated complex.
Translated from Acta Chimica Sinica, 2006, 64(15): 1517–1522 (in Chinese) 相似文献
19.
We report the reactivity of three binuclear non-heme Fe(III) compounds, namely [Fe 2(bbppnol)(μ-AcO)(H 2O) 2](ClO 4) 2 ( 1), [Fe 2(bbppnol)(μ-AcO) 2](PF 6) ( 2), and [Fe 2(bbppnol)(μ-OH)(Cl) 2]·6H 2O ( 3), where H 3bbppnol = N, N′-bis(2-hydroxybenzyl)- N, N′-bis(2-methylpyridyl)–1,3-propanediamine-2-ol, toward the hydrolysis of bis-(2,4-dinitrophenyl)phosphate as models for phosphoesterase
activity. The synthesis and characterization of the new complexes 1 and 3 was also described. The reactivity differences observed for these complexes show that the accessibility of the substrate
to the reaction site is one of the key steps that determinate the hydrolysis efficiency. 相似文献
20.
A neutral tetradentate ligand L1 [L1?=?3,6-bis(pyrazol-1-yl)-pyridazine] reacts with Ni(ClO4)2·6H2O and undergoes counterion exchange with PF
?6
to give di- and tetranuclear complexes [Ni2(L1)2(CH3CN)4](PF6)4·4H2O (1) and [Ni4(L1)4(µ-OH)4](ClO4)4·2H2O (2), respectively. The presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as base controls the nuclearity of the complex formation. Both complexes were structurally characterized by physicochemical and spectroscopic techniques. Their crystal structures revealed that both complexes are centrosymmetric and adopt slightly distorted octahedral geometry. Complex 1 crystallizes in monoclinic space group C2/c as the Ni(II) center is octahedrally bound to L1 in a trans-isomer arrangement. Complex 2 crystallizes in tetragonal space group I41/amd with four L1 and four hydroxy bridging ligands linked to Ni(II) center in cis-isomer arrangement. Cyclic voltammograms of complexes 1 and 2 were measured under Ar and CO2. Under CO2, the quasireversible peaks of both complexes become irreversible and a current enhancement occurs under reduction. 相似文献
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