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1.
Three novel tripodal ligands, N,N′,N′′-tri-(3′-phenylpropionic acid-2′-yl-)-1,3,5-triaminomethylbenzene (Ll), N,N′,N′′-tri-(4′-methylvaleric acid-2′-y1-)-1,3,5-triaminomethylbenzene (L2) and N,N′,N′′-tri-(3′methylvaleric acid-2′-yl-)-1,3,5-triaminomethylbenzene (L3), have been synthesized and fully characterized. The
stabilizing ability of complexes of the three ligands with transition metal ions Cu(II), Ni(II), Zn(II) and Co(II) and rare
earth metal ions La(III), Nd(III), Sm(III), Eu(III) and Gd(III) has been investigated by the pontentiometric method in water
and in aqueous KNO3 (0.1 mol dm−3) at 25.0±0.1 °C, respectively. The results show that there is a great deal of difference between two series of complexes’
stabilities. An explanation of the difference has been given. 相似文献
2.
Three new vic-dioxime ligands, [N-(ethyl-4-amino-1-piperidine carboxylate)-phenylglyoxime (L1H2), N-(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L2H2), and N,N′-bis(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L3H2)], and their Co(II) with Cu(II) metal complexes, were synthesized for the first time. Mononuclear complexes of these ligands
with a 1:2 metal-ligand ratio were prepared with Co(II) and Cu(II) salts. The BF2+-capped Co(II) and mononuclear complexes of the vic-dioxime were prepared for [Co(L1·BF2)2] and [Co(L2·BF2)2]. The ligands act in a polydentate fashion bonding through nitrogen atoms in the presence of a base, as do most vic-dioximes. The cobalt(II) and copper(II) complexes are non-electrolytes as shown by their molar conductivities (ΛM) in DMF. The structures of the ligands and complexes were determined by elemental analyses, FT-i.r., u.v.–vis., 1H- and 13C-n.m.r. spectra, magnetic susceptibility measurements, and molar conductivity. The comparative electrochemical studies show
that the stabilities of the reduced or oxidized species and the electrode potentials of the complexes are affected by the
substituents attached on the oxime moieties of the complexes. 相似文献
3.
Two multidentate ligands: N,N′-di-(propionic acid-2′-yl-)-2,9-di-aminomethylphenanthroline (L1) and N,N′-di-(3′-methylbutyric acid-2′-yl-)-2,9-di-amino-methylphenanthroline (L2) were synthesized and fully characterized by 1H NMR and elemental analysis. The binding ability of L1 and L2 to metal ions such as M(II) (M = Cu, Zn, Co and Ni) and Ln(III) (Ln = La, Nd, Sm, Eu, and Gd) has been investigated by potentiometric
titration in aqueous solution and 0.1 mol dm−3KNO3 at 25.0 ± °C. In view of the structure of L1 and L2, mononuclear metal complexes can be formed in solution. The stability constants of binary complexes of ligands L1 and L2
with metal ions M(II) and Ln(III) have been determined respectively and further discussed. 相似文献
4.
Hassan Keypour Reza Azadbakht Hadi Amiri Rudbari Alireza Heydarinekoo Hamidreza Khavasi 《Transition Metal Chemistry》2009,34(8):835-839
Three new potentially hexadentate N4O2 Schiff-base ligands (H2L1, H2L2 and H2L3) were prepared from the reaction of the polyamines N,N′-bis(2-aminophenyl)-1,2-ethanediamine (L1), N,N′-bis(2-aminophenyl)-1,3-propanediamine (L2) and N,N′-bis(2-aminophenyl)-1,4-butanediamine (L3), respectively with salicylaldehyde. Reaction of the Schiff bases with Ni(II) salts in the presence of N(Et)3 gave the neutral complexes [NiL4], [NiL5] and [NiL6]. Ni(II) complexes of the polyamines were also prepared. One of complexes [Ni(L1)(MeCN)2](ClO4)2·MeCN has been characterized through X-ray diffraction methods. 相似文献
5.
Murat Taş Seval Çamur Yalçın Kılıç 《Journal of Thermal Analysis and Calorimetry》2011,103(3):995-1000
The complexes were synthesized by the reaction between sodium salt of p-aminosalicylic acid (PAS) and Cu(II) for 1 and corresponding ethylenediamine (en) or its derivatives for 2–6. The complexes were characterized by using elemental analyses, FT-IR, UV–Vis, magnetic moment measurements, and thermal analyses
techniques. In complex 1[Cu2(PA)4(H2O)2], two Cu(II) ions were found as bridged by four μ-O:O′ p-aminosalicylato (PA) ligands, forming a cage structure, and two aqua ligands to form dinuclear square-pyramidal geometry
around Cu(II) ions. In the complexes 2–6, the PA (anionic form of p-aminosalicylic acid) coordinated to Cu(II) ions as monodentate manner by using its oxygen atom of deprotonated carboxylic
acid and ethylenediamine derivatives coordinated to the Cu(II) ions in bidentate manner to form mononuclear octahedral complexes
[Cu(PA)2(L)2] (L = ethylendiamine, N,N-dimethylethylendiamine, N,N′-dimethylethylendiamine, N,N,N′,N′-tetramethylethylendiamine, and 1,3-propanediamine, for complexes 2, 3, 4, 5, and 6, respectively). In all the complexes OH and NH2 groups of PA ligands were not coordinated to metals. 相似文献
6.
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
7.
B. Venkateswara Rao 《Journal of Thermal Analysis and Calorimetry》2010,100(2):577-587
Co(II), Ni(II), Cu(II) and Cd(II) chelates with 1-aminoethylidenediphosphonic acid (AEDP, H4L1), α-amino benzylidene diphosphonic acid (ABDP, H4L2), 1-amino-2-carboxyethane-1,1-diphosphonic acid (ACEDP, H5L3), 1,3-diaminopropane-1,1,3,3-tetraphosphonicacid (DAPTP, H8L4), ethylenediamine-N,N′-bis(dimethylmethylene phosphonic)acid (EDBDMPO, H4L5), O-phenylenediamine-N,N′-bis(dimethyl methylene phosphonic)acid (PDBDMPO, H4L6), diethylene triamine-N,N,N′,N′,N″N″-penta(methylene phosphonic)acid (DETAPMPO, H10L7) and diethylene triamine-N,N″-bis(dimethyl methylene phosphonic)acid (DETBDMPO, H4L8) have been synthesised and were characterised by elemental and thermal analyses as well as by IR, UV–VIS, EPR and magnetic
measurements. The first stage in the thermal decomposition process of these complexes shows the presence of water of hydration,
the second denotes the removal of the coordinated water molecules. After the loss of water molecules, the organic part starts
decomposing. The final decomposition product has been found to be the respective MO·P2O5. The data of the investigated complexes suggest octahedral geometry with respect to Co(II) and Ni(II) and tetragonally distorted
octahedral geometry with respect to Cu(II). Antiferromagnetism has been inferred from magnetic moment data. Infrared spectral
studies have been carried out to determine coordination sites. 相似文献
8.
An interesting series of cobalt(II) complexes of the new ligands: 4[N-(benzalidene)amino]antipyrinethiosemicarbazone (BAAPTS), 4[N-(2′-hydroxy-benzalidene)amino]antipyrinethiosemicarbazone (HBAAPTS) and 4[N-(2′-hydroxy-1′-naphthalidene)amino]antipyrinethiosemicarbazone (HNAAPTS) were synthesized by reaction with Co(II) salts in
ethanol. The general stoichiometry of the complexes was found to be [CoX2(H2O)(L)] and [Co(L)2](ClO4)2, where X = Cl, NO3, NCS or CH3COO and L = BAAPTS, HBAAPTS or HNAAPTS. The complexes were characterized by elemental analysis, molar conductivity measurement,
molecular weight determination, magnetic moments at room temperature, infrared and electronic spectra. All the thiosemicarbazones
behave as neutral tridentate (N, N, S) donor ligands. The conductivity measurements in PhNO2 solution indicated that the chloro, nitrato, thiocyanato and acetate complexes are essentially non-electrolytes, while the
perchlorate complexes are 1:2 electrolytes. Thermogravimetric studies were performed for some representative complexes and
the decomposition mechanism proposed. Antibacterial and antifungal properties of the ligands and their cobalt(II) complexes
have also been examined and it has been observed that the complexes are more potent bactericides than the ligand. 相似文献
9.
Summary 2,3-Bis(hydroxyimino)-1,2,3,4-tetrahydro-pyrido[2,3-b]pyrazine (H2L), prepared from 2,3-diaminopyridine and cyanogen-di-N-oxide has been converted into nickel(II), palladium(II), copper(II), cobalt(II), and cobalt(III) complexes (H2L) with a 12 metal:ligand ratio. The ligands coordinate through the two N atoms, as do most vicinal dioximes. [(LH)Cl(H2O)Cd], contains a six-membered chelate ring. [Co(HL)2(L)Cl] has also been prepared using triphenylphosphine, triphenylarsine, thiophene and chloride as axial ligands. The structure of thevic-dioxime and its complexes are proposed on the basis of elemental analysis, i.r.,1H-n.m.r. and uv-visible measurements. 相似文献
10.
Seikh Jasimuddin 《Transition Metal Chemistry》2006,31(6):724-729
Dechlorination of M(RaaiR′)
n
Cl2 by AgNO3 produced [M(RaaiR′)
n
(MeCN)2]+2 [M = Ru(II), n = 2; Pt(II), n = 1; RaaiR′ = 1-alkyl-2-(arylazo)imidazole)] which upon reaction with the nucleobase cytosine (C) in MeCN solution gave cytosinato
bridged dimeric compounds which were isolated as perchlorate salts [M2(RaaiR′)
n
(C)2](ClO4)2 · H2O. The products were characterized by IR, u.v.–vis., 1H-n.m.r. spectroscopy and cyclic voltammetry. In MeCN solution the ruthenium complexes exhibit a strong MLCT band at 550–555 nm
and two redox couples positive to SCE due to two metal-center oxidation along with ligand reduction, negative to SCE. The
platinum complexes show a weak transition at 500–520 nm in MeCN and exhibit only ligand reduction in cyclic voltammetry. The
coordination of the ligand was supported by 1H-n.m.r. spectral data. 相似文献
11.
Subhi A. Al-Jibori Ali I. Abdullah Talal A. K. Al-Allaf 《Transition Metal Chemistry》2007,32(3):398-406
Palladium(II) and platinum(II) complexes containing mixed ligands N-(2-pyridyl)acetamide (AH) or N-(2-pyrimidyl)acetamide (BH) and the diphosphines Ph2P(CH2)
n
PPh2, (n = 1, 2 or 3) have been prepared. The prepared complexes [Pd(A)2(diphos)] or [Pd(B)2(diphos)] have been used effectively to prepare bimetallic complexes of the type [(diphos)Pd(μ-L)2M′Cl2] where M′ = Co, Cu, Mn, Ni, Pd, Pt or SnCl2; L = A or B. The prepared complexes were characterized by elemental analysis magnetic susceptibility, i.r. and UV–Vis spectral
data. 31P–{1H}-n.m.r. data have been applied to characterize the produced linkage isomers. 相似文献
12.
Yang Guang Ji Liang-Nian Zhou Xiang-Ge Zhou Zhong-Yuan 《Transition Metal Chemistry》1998,23(3):273-276
Two ruthenium(II) complexes with polypyridyl ligands, [Ru(bpy)2(AFO)](ClO4)2 · H2O (1) and [Ru(dmp)2 (AFO)](ClO4)2 · 1/2DMF · 1/2MeCN (2) (bpy = 2,2′-bipyridine; dmp = 2,9-dimethyl-1,10-phenanthroline; AFO = 4,5-diazafluoren-9-one; DMF = N,N-dimethylformamide), were synthesized and characterized by elemental analyses, i.r. and u.v.-vis. spectra. The structures
of the two complexes were determined by single crystal X-ray diffraction techniques. To relieve ligand interaction, the coordination
sphere is distorted so as to form specific angles (δ) between the polypyridyl ligand planes and coordination planes (N-Ru-N).
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
13.
In the compound [Ni(Bptc)2(Bimb)2(H2O)2] (I), where H4Bptc is 3,3′,4,4′-biphenyltetracarboxylic acid; Bimb is 4,4′-bis(1-imidazolyl)biphenyl), Ni(II) has a distorted octahedral coordination geometry, which was bonded with two N atoms from two
Bimb ligands, two O atoms from two H2Bptc2− ligands and two water O atoms. The crystal structure of compound I is stabilized by the π-π-stacking and hydrogen bonds interaction. 相似文献
14.
A zwitterionic trichloroplatinum(II) complex PtCl3(4,4′-bpy-N-nBu) (1) was prepared by an aqueous reaction of [4,4′-bpy-N-nBu]Cl with K2PtCl4, and was characterized by 1H-n.m.r. and IR spectroscopy as well as elemental analysis. Dissolving (1) into dmso-d
6 at 25 °C yields a mixture of the complexes, cis-PtCl2(4,4′-bpy-N-nBu)(dmso-d
6) (2-cis), trans-PtCl2(4,4′-bpy-N-nBu)(dmso-d
6) (2-trans), [4,4′-bpy-N-nBu]Cl and PtCl2(dmso-d
6)2. Ratio of the products in the dmso-d
6 solution changed depending on the temperature and the total concentration of the complexes. These compounds are in equilibrium
via isomerization reaction between (2-cis) and (2-trans) and via displacement reaction of the alkylbipyridinium ligand of
(2-cis) and (2-trans) with dmso-d
6 to form [4,4′-bpy-N-nBu]Cl and PtCl2(dmso-d
6)2. 相似文献
15.
Mozaffar Asadi Maryam Mohammadikish Khosro Mohammadi 《Central European Journal of Chemistry》2010,8(2):291-299
Four Schiff base ligands, salabza-H2 = N,N′-bis(salicylidene)-2-aminobenzylamine, were synthesized by condensation of one mole of 2-aminobenzylamine and two moles of
salicylaldehyde and/or two moles of substituted salicylaldehyde (5-OMe, 5-Br, 5-NO2). All the four Schiff bases and their Mn(II), Co(II), Cu(II) and Zn(II) complexes are characterized by UV-Vis, FT-IR, 1H NMR spectroscopy, mass spectrometry and elemental analysis. The formation constants and the Gibbs free energies were measured
spectrophotometrically for 1:1 complexes in methanol in constant ionic strength (I = 0.1 mol dm−3 NaClO4) and at 25°C. The data refinement was carried out with the SQUAD program. The trend of formation constants of H2L1 with M(II) follows the order: Mn(II) (3.97) < Zn(II) (4.30) < Co(II) (4.89) < Cu(II) (5.73) 相似文献
16.
Frank Marken Alastair N. Blythe Jay D. Wadhawan Richard G. Compton Steven D. Bull Robin T. Aplin Stephen G. Davies 《Journal of Solid State Electrochemistry》2001,5(1):17-22
The effect of the structure of the organic precursor molecule on the electroinsertion of anions and on the formation of materials
in the ionic liquid state is compared for three compounds, para-N, N, N′, N′-tetrahexylphenylenediamine (p-THPD), meta-N, N, N′, N′-tetrahexylphenylene diamine (m-THPD), and para-N, N, N′, N′-tetrakis(6-methoxyhexyl)phenylenediamine (p-TMHPD), by characterising their condensed phase voltammetric properties in aqueous media. The electrochemically driven anion
insertion in p-THPD and p-TMHPD in the presence of ClO4
−, F−, Cl−, Br−, I−, and SO4
2− is shown to be extremely sensitive to structure. The introduction of the methoxy end groups in p-TMHPD causes (1) a considerable shift to more negative electroinsertion potentials, (2) a less stable response which upon
continuous cycling decreases, and (3) considerably lower anion selectivity. For the insertion of sulfate, only p-TMHPD yields an electrochemical response which is shown to be consistent with insertion of the dianion SO4
2−. The electrochemical oxidation of a deposit of m-THPD is accompanied by anion insertion and a chemical reaction step in an EC-type electrochemical process. The product of
the chemical step is electrochemically active and results in a new reversible electroinsertion process. Starting materials
and products of the microdroplet reactions are characterised by Maldi-TOF mass spectrometry and a reaction mechanism based
on condensed phase polymerisation is proposed.
Received: 15 November 1999 / Accepted: 2 December 1999 相似文献
17.
A u.v.–vis spectrophotometric study of the adduct formation of the nickel(II) Schiff base complexes,([NiL]) where L = [3-methoxysalophen,
N,N′-bis(3-methoxysalicylidene)-1,2-phenylenediimine] (1), [4-methoxysalophen, N,N′-bis(4-methoxysalicylidene)-1,2-phenylenediimine] (2), [5-methoxysalophen, N,N′-bis(5-methoxysalicylidene)-1,2-phenylenediimine] (3) and [Salophen, [N,N′-bis(salicylaldehydo)-1,2-phenylenediimine] (4) as donors with R2SnCl2 (R = methyl, phenyl and n-butyl) as acceptors have been investigated in chloroform, as solvent. Adducts have been characterized by 1H, 13C and 119Sn NMR, IR and electronic spectroscopy and CHN elemental microanalysis. The formation constants and the thermodynamic free
energies were measured using u.v.–vis spectrophotometry titration for 1:1 adduct formation at various temperatures (T = 278
to 308 K). The trend of the adduct formation of the nickel Schiff base complexes with a given tin acceptor decreases as follows:
and
The trend of the reaction of R2SnCl2 acceptors toward a given nickel Schiff base complex is as follows:
相似文献
18.
Alfonso Castiñeiras María Consuelo F. Vidal Rosa Carballo 《Transition Metal Chemistry》1995,20(5):477-480
Summary The coordination behaviour of N,N-bis(1-carboxymethyl)dithioxamide (GLYDTO), N,N-bis(1-carboxyethyl)dithioxamide (ALADTO), N,N-bis(1-carboxy-2-methylpropyl) dithioxamide (VALDTO) and N,N-bis(1-carboxy-3-methylbutyl)dithioxamide (LEUDTO) has been investigated by isolating and characterizing the dinuclear, neutral cobalt(II) complexes, [Co2(L-4H)(H2O)2] (L = GLYDTO, ALADTO, VALDTO or LEUDTO) and [Co2(L-4H)(H2O)6] (L = ALADTO or VALDTO). All ligands were characterized by mass, i.r., and 1H- and 13C-n.m.r. spectroscopy. The complexes possess distorted octahedral structures as revealed by the magnetic and electronic (diffuse reflectance) spectral data. The i.r. data indicate that the ligands are bis-tridentate, bis-dianions coordinated to each metal ion through the carboxylate oxygen, deprotonated thioamide nitrogen and thiocarbonyl sulphur atoms. 相似文献
19.
A fully deprotonated 2-bromo-1,4-benzenedicarboxylate copper(II) complex, [Cu(bbdc)(2,2′-bipy)](H2O) (bbdc= 2-bromo-1,4-benzenedicarboxylate dianion, 2,2′-bipy=2,2′-bipyridine), was synthesized under hydrothermal conditions.
This compound also can be prepared from the partly deprotonated [Cu(Hbbdc)2(2,2′-bipy)] under basic and hydrothermal conditions. The crystal structure consists of infinite chains of [Cu2(μ4-bbdc)]2+ building blocks connected by bis-monodentate bbdc ligands and exhibits an extended 2-D architecture.
Electronic supplementary material Electronic supplementary material is available for this article at
and accessible for authorised users. 相似文献
20.
A series of hybrid mesoporous SBA-15 materials containing four iron(III) Schiff base complexes of the type [FeL
x
(NO3)] (x = 4–7, L = N,N′-bis(salicylidene)ethylenediamine, N,N′-bis(salicylidene)diethylenetriamine, N,N′-bis(salicylidene)o-phenylenediamine, N,N′-bis(3-nitro-salicylidene)ethylenediamine) was synthesized by a post-grafting route. The XRD, N2 adsorption/desorption and TEM measurements confirmed the structural integrity of the mesoporous hosts, and the spectroscopic
characterization techniques (FT-IR, UV–vis spectroscopy, 1H NMR) confirmed the ligands and the successful anchoring of iron(III) Schiff base complexes over the modified mesoporous
support. Quantification of the supported ligand and metal was carried out by TG/DSC and ICP-AES techniques. The catalyst FeL7-SBA resulting from N,N′-bis(3-nitro-salicylidene)ethylenediamine) ligand was considerably active for the aerobic epoxidation
of styrene, in which the highest conversion of styrene reached 83.6%, and the selectivity to styrene oxide was 83.0%. Moreover,
it was also found that the catalytic activity increases with the decrease in the electron-donating ability of the Schiff bases,
and the selectivity varies according to the types of substituents in the ligands. 相似文献