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1.
Two new cobalt(III) complexes of the Schiff base N,N′-disalicylidene-1,2-phenylendiimine dianion (salophen), trans- [CoIII(salophen)(ta)2]ClO4, (ta = thioacetamide) (1) and trans-[CoIII(salophen)(tb)2]ClO4, (tb = thiobenzamide) (2) were synthesized and characterized using single-crystal X-ray diffraction and spectroscopic techniques. Both complexes show solvatochromism in a variety of solvents. Complex (1) crystallized from CHCl3 as a solvate of orthorhombic symmetry, space group Pca21 with a = 17.3480(10) Å, b = 18.7522(10) Å, c = 18.8128(11) Å, α = β = γ = 90°, and Z = 8. The cobalt(III) center lies in a distorted octahedral environment. The crystal structure of (1) consists of two independent [CoIII(salophen)(ta)2]+ cations and ClO4 - anions held together essentially via hydrogen bonds and π-π stacking interactions. Complex (2), forming also a CHCl3 solvate, crystallized in the monoclinic space group P21/n with a = 14.710(3) Å, b = 13.506(3) Å, c = 18.595(4) Å, β = 100.295(4)°, and Z = 4. The geometry around cobalt(III) center is a distorted octahedron. The crystal structure of (2) contains a [CoIII(salophen)(tb)2]+ complex with a remarkably twisted salophen ligand. Both complexes, (1) and (2), contain approximately one disordered CHCl3 molecule per Co in the solid state.  相似文献   

2.
Trinuclear mixed-valence Co(III)-Co(II)-Co(III) complex {CoIII(μ-Sal2MePn)(N3)(μ1,1-N3)}2CoII(H2O)2 (I) was synthesized by the reaction of Co(NO3)2 · 6H2O with the Schiff base ligand H2Sal2MePn condensed from 2,2-dimethylpropylenediamine with salicylaldehyde and characterized by elemental analyses and FT-IR spectroscopy. The molecular structure of I has been determined from single-crystal X-ray diffraction analysis. In this structure, the N3 anions show both terminal and μ1,1-bridging modes. The terminal Co(III) centers exhibit uniform arrangements of the Schiff-base ligand and N3 anions.  相似文献   

3.
The reactions of 5-R-2-hydroxybenzaldehyde-4-allyl-thiosemicarbazone {R: H (L1); Br (L2)} with [MII(PPh3)nCl2] (M = Ni, n = 2 and M = Ru, n = 3) in a 1:1 molar ratio have given stable solid complexes corresponding to the general formula [Ni(L)(PPh3)] and [Ru(HL)2(PPh3)2]. While the 1:1 nickel complexes are formed from an ONS donor set of the thiosemicarbazone and the P atom of triphenylphosphine in a square planar structure, the 1:2 ruthenium complexes consist of a couple from each of N, S and P donor atoms in a distorted octahedral geometry. These mixed-ligand complexes have been characterized by elemental analysis, IR, UV–Vis, APCI-MS, 1H and 31P NMR spectroscopies. The structures of [Ni(L2)(PPh3)] (II) and [Ru(L1H)2(PPh3)2] (III) were determined by single crystal X-ray diffraction.  相似文献   

4.
Double complex salts (DCSs) [Co(NH3)6][Fe(CN)6] (I) and [Co(NH3)6]2[Cu(C2O4)2]3 (II) and complex [Co(NH3)6]2(C2O4)3·4H2O (III) are synthesized and investigated by single crystal XRD, crystal optics, and elemental analysis. The crystalline phases of I, II, and III (R-3, P21/c, and Pnnm space groups respectively) have the following crystallographic characteristics: a = 10.9804(2) ?, b = 10.9804(2) ?, c = 10.8224(3) ?, V = 1130.03(4) ?3, Z = 3, d x = 1.65 g/cm3 (I); a = 9.6370(2) ?, b = 10.2452(2) ?, c = 13.2108(3) ?, V = 1932.90(9) ?3, Z = 2, d x= 1.97 g/cm3 (II), and a = 11.7658(3) ?, b = 11.7254(3) ?, c = 14.1913(4) ?, V = 1304.34(5) ?3, Z = 2, d x = 1.68 g/cm3 (III). This paper investigates the products of DCS thermolysis in a hydrogen atmosphere: the intermetallic compound CoFe with the bcc parameter a = 2.852 ? for I and a heterogeneous mixture of Co and Cu in the decomposition of II. The coordinated CN and C2O42− groups then turn into NH3, hydrocarbons, and CO2. The dominant hydrocarbon is methane.  相似文献   

5.
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.  相似文献   

6.
Decavanadates with complex cations, (NH4)2[Zn(H2O)5(NH3CH2CH2COO)]2V10O28·4H2O (4) and (NH4)2[Mn(H2O)5(NH3CH2CH2COO)]2V10O28·2H2O (5), have been prepared and characterized by elemental analysis, i.r., Raman, UV–vis. and 51V-n.m.r. spectroscopies and by thermal analysis. The X-ray structure determination revealed, both in 4 and 5, the presence of complex cations with hexacoordinated central atoms and monodentate β-alanine ligands, and decavanadate V10O28 6− anions. The differences in the structural arrangement in 4 and 5 are probably a consequence of the different ionic radii of Zn2+ and Mn2+ (high spin).  相似文献   

7.
The synthesis and characterization of a series of cobalt(III) complexes of the general type [Co(N2O2)(L2)]+ are described. The N2O2 Schiff base ligands used are Me-salpn (H2Me-salpn = N,N′-bis(methylsalicylidene)-1,3-propylenediamine) (13) and Me-salbn (H2Me-salbn = N,N′-bis(methylsalicylidene)-1,4-butylenediamine) (45). The two ancillary ligands L include: pyridine (py) 1, 3-metheylpyridine (3-Mepy) 2, 1-methylimidazole (1-MeIm) 3, 4-methylpyridine (4-Mepy) 4 and pyridine (py) 5. These complexes have been characterized by elemental analyses, IR, UV–Vis, and 1H NMR spectroscopy. The crystal structures of trans-[CoIII(Me-salpn)(py)2]PF6, 1, and cis-α-[CoIII(Me-salbn)(4-Mepy)2]BPh4 · 4-Mepy, 4, have been determined by X-ray diffraction. Examination of the solution and crystalline structures revealed that the outer coordination sphere of the complexes exerts a noticeable influence on the inner coordination sphere of the Co(III) ion. The electrochemical reduction of these complexes at a glassy carbon electrode in acetonitrile solution indicates that the first reduction process corresponding to CoIII–CoII is electrochemically irreversible, which is accompanied by the dissociation of the axial (R-py)–cobalt bonds. It has also been observed that the Co(III) state is stabilized with increasing the flexibility of the ligand environment.  相似文献   

8.
Syntheses and structure determination of TbIII and ErIII complexes with nitrilotriacetic acids (nta) are reported. Their crystal and molecular structures, molecular formulas, and compositions were determined by single-crystal X-ray structure analyses and elementary analyses, respectively. The crystal of the (NH4)3[TbIII(nta)2(H2O)]·4H2O complex belongs to the monoclinic crystal system and C2/c space group. Crystal data are as follows: a = 16.357(8) Å, b = 8.552(4) Å, c = 17.390(9) Å, β = 104.748(7)°, V = 2352.6(19) Å3, Z = 4, Mr = 675.32, Dc = 1.932 g·cm−3, μ = 3.112 mm−1, and F(000) = 1368. The final R and Rw are 0.0220 and 0.0494 for 2357 (I > 2σ(I)) unique reflections, R and Rw are 0.0266 and 0.0510 for all 5613 reflections, respectively. The TbIIIN2O7 moiety in the [TbIII(nta)2(H2O)]3− complex anion has a pseudo-monocapped square antiprismatic nine-coordinate structure, in which the eight coordinate atoms (two N and six O) are from two nta ligands and the water molecule is coordinated to the central TbIII ion directly as the ninth coordinate atom. The crystal of the (NH4)3[ErIII(nta)2] complex belongs to the trigonal crystal system and R-3c space group. Crystal data are as follows: a = 7.9181(16) Å, b = 7.9181(16) Å, c = 54.27(2) Å, γ = 120°, V = 2946.7(14) Å3, Z = 6, Mr = 597.61, D c = 2.021 g·cm−3, μ = 4.345 mm−1, and F(000) = 1770. The final R and Rw are 0.0295 and 0.0673 for 677 (I > 2σ(I)) unique reflections, R and Rw are 0.0366 and 0.0700 for all 4827 reflections, respectively. The ErIIIN2O6 part in the [ErIII(nta)2]3− complex anion is an eight-coordinate structure with a pseudo-dicapped octahedron, in which the eight coordinate atoms (two N and six O) are from two nta ligands.Original Russian Text Copyright © 2004 by J. Wang, X. D. Zhang, Y. Wang, Y. Zhang, Z. R. Liu, J. Tong, and P. L. Kang__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1067–1075, November–December, 2004.  相似文献   

9.
The structure, spectroscopic, and electrochemical properties of [Co{(BA)2pn}(L)2]ClO4 complexes, where (BA)2pn = N,N′-bis(benzoylacetone)-1,3-propylenediimine dianion and the two ancillary ligands (L) are pyridine, py (1), and 4-methylpyridine, 4-Mepy (2), have been investigated. These complexes have been characterized by elemental analyses, IR, UV–Vis and 1H-NMR spectroscopy. The crystal structure of [Co{(BA)2pn}(py)2]ClO4 (1) has been determined by X-ray diffraction. The coordination geometry around cobalt(III) is best described as a distorted octahedron. The electrochemical reduction of these complexes at a glassy carbon electrode in acetonitrile solution indicates that the first reduction process corresponding to CoIII–CoII is electrochemically irreversible, which is accompanied by the dissociation of the axial N(py)–cobalt bonds. This process becomes quasi-reversible upon the addition of excess py ligands. The second reduction step of CoII/I shows reversible behavior and is not influenced by the nature of the axial ligands. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

10.
The dissolution of DyI2 in diamine Me2N(CH2)3NH2 (DMDA) is accompanied by the disproportionation of the salt, hydrogen evolution, and oxidation of DyII to DyIII. The [Dy(DMDA)8]I3 complex (1) was isolated from the solution. The neodymium amide amine complex (PriNH)NdI2(IPA)4 was produced by the reaction of NdI2 with isopropylamine (IPA). The recrystallization of this complex from IPA afforded the NdI3(IPA)4 complex (2). The recrystallization of (PriNH)NdI2(IPA)4 from a toluene-IPA mixture gave the complex with five amine ligands, NdI3(IPA)5 (3). The structures of compounds 1, 2, and 3 were established by X-ray diffraction. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1674–1679, September, 2007.  相似文献   

11.
The reactions of [RuHCl(CO)(PPh3)3] and [(C6H6)RuCl2]2 with 2-benzoylpyridine have been examined, and two novel ruthenium(II) complexes – [RuCl(CO)(PPh3)2(C5H4NCOO)] and [RuCl2(C12H9NO)2] – have been obtained. The compounds have been studied by IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis.  相似文献   

12.
A procedure was developed for the synthesis of trinuclear cyclic (ZrIII)2—Al hydrides [(Cp2Zr)2(μ-H)](μ-H)2AlX2 (X = Cl (1a) or Br (1b)). These complexes were prepared in 60–65% yields by the reaction of Cp2ZrX2 with LiAlH4 in the presence of CoBr2 and tolane. The structures of complexes 1a and 1b and iodide 1c (X = I) were studied by NMR spectroscopy in solvents of different basicities (toluene, THF, and pyridine). Complex 1a is unsolvated and monomeric in all solvents; complex 1b, in toluene and THF; complex 1c, in toluene only. At room temperature, complex 1a does not catalyze hydrogenation of hex-1-ene and does not react with tolane, but reacts with the latter at high temperature to give bis(η5-cyclopentadienyl)-2,3,4,5-tetraphenylzirconacyclopentadiene. The reaction of equivalent amounts of complex 1a and HCl produces the [(Cp2Zr)2(μ-Cl)](μ-H)2AlCl2 complex. The structure of the latter was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2418–2423, November, 2005.  相似文献   

13.
The reactions of lanthanide tris(borohydrides) Ln(BH4)3(thf)3 (Ln = Sm or Nd) with 2 equiv. of lithium N,N′-diisopropyl-N′-bis(trimethylsilyl)guanidinate in toluene produced the [(Me3Si)2NC(NPri)2]Ln(BH4)2Li(thf)2 complexes (Ln = Sm or Nd), which were isolated in 57 and 42% yields, respectively, by recrystallization from hexane. X-ray diffraction experiments and NMR and IR spectroscopic studies demonstrated that the reactions afford monomeric ate complexes, in which the lanthanide and lithium atoms are linked to each other by two bridging borohydride groups. The complexes exhibit catalytic activity in polymerization of methyl methacrylate. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–445, March, 2007.  相似文献   

14.
A new macrocyclic ligand, 1,3,5-triaza-2,4:7,8:15,16-tribenzo-9,15-dioxacycloheptadeca-1,5-diene (L) was synthesized by reaction of 2,6-diaminopyridine with 1,4-bis(2-carboxyaldehydephenoxy)butane. Then, its CuII, NiII, PbII, CoIII and LaIII complexes were synthesized by the template effect by reaction of 2,6-diaminopyridine and 1,4-bis (2-carboxyaldehydephenoxy)butane and Cu(NO3)2 · 3H2O, Ni(NO3)2 · 6H2O, Pb(NO3)2, Co(NO3)2 · 6H2O, La (NO3)3 · 6H2O, respectively. The ligand and its metal complexes were characterized by elemental analysis, IR, 1H- and 13C-n.m.r., UV-vis spectra, magnetic susceptibility, thermal gravimetric analysis, conductivity measurements and mass spectra. All complexes are diamagnetic and the CuII complex is binuclear. The CoII complex was oxidised to CoIII.  相似文献   

15.
Two new ruthenium(Ⅱ) complexes, [Ru(btz)3](ClO4)2 (1) and [Ru(btz)(dppz)2](ClO4)2 (2) (btz = 4,4′-bithi-azole, dppz = dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized and characterized by elemental analysis, 1H NMR, ES-MS and X-ray crystallography. The DNA binding behaviors of two complexes have been studied by spectroscopic and viscosity measurements. The results suggest that complex 1 binds to CT-DNA via an electrostatic mode, while complex 2 via an intercalative mode. Under irradiation at 365 nm,...  相似文献   

16.
Adducts of cucurbit[6]uril with Ca2+ and trinuclear cluster chloroaquacomplexes (H9O4)2(H7O3)2[(Ca(H2O)5)2(C36H36N24O12)]Cl8·0.67H2O (1) and [(Ca(H2O)5)2(C36H36N24O12)]× [Mo3O2S2Cl6(H2O)3]2·13H2O (2) are obtained and structurally characterized. The structures of both compounds contain polymeric [Ca(H2O) n ]22 CB[6]∞ cations that form infinite columns; the space between them is filled with Cls- (1) and [Mo3O2S2Cl6(H2O)3]2s- (2). A new (H7O3)2(H5O2)× [Mo3S4Cl6.25Br0.25(H2O)2](C36H36N24O12)·CH2Cl2·6H2O complex (3) is also obtained and structurally characterized.  相似文献   

17.
The singlet-triplet separations for the edge-sharing bioctahedral (ESBO) complex W2(μ-H)(μ-Cl)(Cl4(μ-dppm)2 · (THF)3 (II) has been studied by 31P NMR spectroscopy. The structural characterization of [W2(μ-H)2(μ-O2CC6H5)2Cl2(P(C6H5)3)2] (I) by single-crystal X-ray crystallography has allowed the comparison of the energy of the HOMOLUMO separation determined using the Fenske-Hall method for a series of ESBO complexes with two hydride bridging atoms, two chloride bridging atoms and the mixed case with a chloride and hydride bridging atom. The complex representing the mixed case, [W2(μ-H)(μ-Cl)Cl4(μ-dppm)2 · (THF)3] (II), has been synthesized and the value of −2J determined from variable-temperature 31P NMR spectroscopy.  相似文献   

18.
Four Co(II) complexes, [Co(HL)2](OAc)2, [Co(HL)2Cl2], [Co(HL)2(MeOH)2](NO3)2, and [Co2(HL)4(SO4)2] (HL = acetone-N(4)-phenylsemicarbazone) were synthesized and characterized by physicochemical and spectroscopic methods. The magnetic susceptibility measurements indicate that the complexes are paramagnetic with three unpaired electrons. In all the complexes, the semicarbazone is coordinated as a neutral bidentate ligand. The structure of [Co(HL)2(MeOH)2](NO3)2 was confirmed by single crystal X-ray crystallography. The ligand is neutral and bidentate, being coordinated to the cobalt atom through the carbonyl oxygen and the azomethine nitrogen. Intermolecular hydrogen bonding and C–H···π interactions combine to stabilize the crystal structure. The ligand and its two complexes [Co(HL)2Cl2] and [Co(HL)2(MeOH)2](NO3)2 were screened for their antibacterial and antifungal activities using disk diffusion methods.  相似文献   

19.
The trimeric, cyclic dimethyltin-containing tungstophophate [{(Sn(CH3)2)(Sn(CH3)2O)(A-PW9O34)}3]21− (1) has been synthesized in aqueous acidic medium and characterized by IR, elemental analysis, electrochemistry, and FT-ICR MS. Single-crystal X-ray analysis was carried out on Cs12Na9[{(Sn(CH3)2)(Sn(CH3)2O)(A-PW9O34)}3]·20H2O (1a), which crystallizes in the trigonal system, space group R3, with a = b = 29.7445(7) ?, c = 15.5915(7) ? and Z = 3. Polyanion 1 is composed of three trilacunary (A-PW9O34) Keggin fragments that are linked on one side via three isolated dimethyltin groups and on the other side by a (Sn3(CH3)6O3) unit and three cesium ions, resulting in a cyclic assembly with C 3v symmetry. The discrete molecular, hybrid organic–inorganic 1 was synthesized by reaction of (CH3)2SnCl2 with Na9[A-PW9O34] in 0.5 M sodium acetate buffer (pH 4.8). Comparison of several characteristics of the cyclic voltammograms of 1 and (A-PW9O34)9−, including the potential location of their reduction peaks, the difference in their current intensities and their qualitative relative electron transfer speeds, supports the conclusion that the solid-state structure of 1 is retained in solution. The presence of (PW9O34)-based species in solutions of 1 was also confirmed by FT-ICR mass spectrometry. Dedicated to Professor Günter Schmid on the occasion of his 70th birthday.  相似文献   

20.
The interaction of the ytterbium bis(indenyl) complex (C9H7)2YbII(THF)2 (1) with the 1,4-diazabutadiene 2-MeC6H4N=C(Me)-C(Me)=NC6H4Me-2 (MeDAD) is accompanied by the oxidation of the metal atom to the trivalent state and results in a paramagnetic compound of the metallocene type (C9H7)2YbIII(MeDAD−·) (3) containing the radical anion of 1,4-diazabutadiene. The structure of the complex 3 was determined by X-ray diffraction analysis. The reactions of the bis(indenyl) (1) and bis(fluorenyl) (C13H9)2YbII(THF)2 (2) derivatives of divalent ytterbium with the 1,4-diazabutadiene PhN=C(Ph)-C(Ph)=NPh (PhDAD) (with the molar ratio of the reactants 1:2) proceed with a complete cleavage of the bonds Yb-C and the oxidation of the ytterbium atom to the trivalent state and result in a homoligand complex (PhDAD−·)3Yb (6) containing three radical anion 1,4-diazadiene ligands. Complex 6 was also obtained by an exchange reaction of YbCl3 with PhDAD−·K+ (1: 3) in THF. Complex 6 was characterized by X-ray diffraction analysis.  相似文献   

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