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1.
We describe the synthesis and characterization of a new tetradentate Schiff base ligand obtained from 2,3-diaminopyridine and 5-methoxysalicylaldehyde. This ligand (H2L) reacted with nickel(II), copper(II), and zinc(II) acetates to give complexes. The ligand and its metal complexes were characterized using analytical, spectral data (UV–vis, IR, and mass spectroscopy), and cyclic voltammetry (CV). The crystal structure of the copper complex was elucidated by X-ray diffraction studies. The electrochemical behavior of these compounds, using CV, revealed that metal centers were distinguished by their intrinsic redox systems, e.g. Ni(II)/Ni(I), Cu(II)/Cu(I), and Zn(II)/Zn(I). Moreover, the electrocatalytic reactions of Ni(II) and Cu(II) complexes catalyze the oxidation of methanol and benzylic alcohol.  相似文献   

2.
Two mononuclear Cu(II) complexes, [Cu(L1H2)](ClO4)1.25Cl0.75·1.25H2O (1) and [Cu(L2H2)](ClO4)2 (2), of the pyridoxal Schiff base ligands N,N′-dipyridoxylethylenediimine (L1H2) and N,N′-dipyridoxyl-1,3-propanediimine (L2H2) are reported. X-ray crystal structures of both complexes are also reported. In both complexes the pyridoxal nitrogen atoms remain protonated. In the solid state, the tetradentate Schiff base ligand is virtually planar in 1, while in 2 the ligand conformation is like an inverted umbrella. In cyclic voltammetry experiments it is found that in these complexes the Cu(III) and Cu(I) states are more easily accessible than in their salen type analogs. The pyridoxal Schiff base complexes are also found to be resistant to oxidative electro-polymerization, unlike their corresponding salicyl aldehyde Schiff base complexes.  相似文献   

3.
Four ruthenium(II) p-cymene complexes with naphthalene-based Schiff base ligands [Ru(p-cymene)LCl] (2a2d) have been synthesized and characterized. The half-sandwich ruthenium complexes were characterized by 1H and 13C NMR spectra, elemental analyses, and infrared spectrometry. The molecular structures of 2a, 2b, and 2c were confirmed by single-crystal X-ray diffraction. Furthermore, these half-sandwich ruthenium complexes are highly active catalysts for the hydrogenation of nitroarenes to anilines using NaBH4 as the reducing agent in ethanol at room temperature.  相似文献   

4.
A series of neutral, anionic and cationic arene ruthenium complexes containing the trichlorostannyl ligand have been synthesised from SnCl2 and the corresponding arene ruthenium dichloride dimers [(η6-arene)Ru(μ2-Cl)Cl]2 (arene = C6H6, PriC6H4Me). While the reaction with triphenylphosphine and stannous chloride only gives the neutral mono(trichlorostannyl) complexes [(η6-C6H6)Ru(PPh3)(SnCl3)Cl] (1) and [(η6-PriC6H4Me)Ru(PPh3)(SnCl3)Cl] (2), the neutral di(trichlorostannyl) complex [(η6-PriC6H4Me)Ru(NCPh)(SnCl3)2] (3) could be obtained for the para-cymene derivative with benzonitrile as additional ligand. By contrast, the analogous reaction with the benzene derivative leads to a salt composed of the cationic mono(trichlorostannyl) complex [(η6-C6H6)Ru(NCPh)2(SnCl3)]+ (5) and of the anionic tris(trichlorostannyl) complex [(η6-C6H6)Ru(SnCl3)3] (6). On the other hand, [(η6-PriC6H4Me)Ru(μ2-Cl)Cl]2 reacts with SnCl2 and hexamethylenetetramine hydrochloride or 18-crown-6 to give the anionic di(trichlorostannyl) complex [(η6-PriC6H4Me)Ru(SnCl3)2Cl] (4), isolated as the hexamethylenetetrammonium salt or the chloro-tin 18-crown-6 salt. The single-crystal X-ray structure analyses of 1, 2, [(CH2)6N4H][4], [(18-crown-6)SnCl][4] and [5][6] reveal for all complexes a pseudo-tetrahedral piano-stool geometry with ruthenium-tin bonds ranging from 2.56 (anionic complexes) to 2.60 Å (cationic complex).  相似文献   

5.
This article describes the preparation and characterization of cis-[Ru(bipy)2L](ClO4)2 and trans-[RuCl2L2]?·?Cl (bipy?=?2,2′-bipyridyl and L?=?ortho-phenylenediamine (o-phd), 2-aminopyridine (2-apy) and 2-aminobenzonitrile (2-abn), and examines the catalytic oxidations of benzyl alcohol, benzohydrol and pipronyl alcohol by cis-[Ru(bipy)2 (o-phd)](ClO4)2 and trans-[RuCl2(o-phd)2]?·?Cl complexes at room temperature and in the presence of N-methyl morpholine-N-oxide (NMO) as co-oxidant.  相似文献   

6.
The chitosan–(Fe(II), Co(II), and Cu(II)) complexes were prepared by mixing chitosan (Chi) powder with a salicylaldehyde (Sal, 5-hydrogen (–H)) and their 5-bromo (–Br), 5-chloro (–Cl), 5-methoxy (–OCH3), 5-fluoro (–F), 5-methyl (–CH3), and 5-nitro (–NO2) derivatives (groups R) and mixing these with FeCl2 and CuCl2 in ethanol and with Co(CH3COO)2 solutions in butanol at 80 °C over 8 h in heterogeneous phase, followed by extraction with ethanol and butanol, respectively. The complexes were characterized by FTIR and UV–vis spectroscopy, elemental analysis, and cyclic voltammetry. A linear correlation between the metal formal potential versus the Hammett parameters of the substituents was observed. The electron-withdrawing groups shift the redox potential to positive values, as a result of lowering the energy of the highest occupied molecular orbital. The formal potential was used as a measurement for the driving force of chitosan complexes for redox reactions.  相似文献   

7.
Treatment of the chiral tripod ligand (LMent,SC)-CpH(PNMent) with (Ph3P)3RuCl2 in ethanol afforded the two chiral-at-metal diastereomers (LMent,SC,RRu)- and (LMent,SC,SRu)-[Cp(PNMent)Ru(PPh3)Cl] (70% de) in which the cyclopentadienyl group and the P atom of the ligand coordinated at the metal center. The (LMent,SC,RRu)-diastereomer was isolated by crystallization from ethanol-pentane and its structure was established by X-ray crystallography. The (LMent,SC,RRu)-diastereomer epimerized in CDCl3 solution at 60 °C in a first-order reaction with a half-life of 5.66 h. In alcoholic solution epimerization occurred at room temperature. Substitution of the chloride ligand in (LMent,SC,RRu)- and (LMent,SC,SRu)-[Cp(PNMent)Ru(PPh3)Cl] by nitriles NCR (R = Me, Ph, CH2Ph) in the presence of NH4PF6 gave mixtures of the diastereomers (LMent,SC,RRu)- and (LMent,SC,SRu)-[Cp(PNMent)Ru(PPh3)NCR]PF6. Treatment of (LMent,SC,RRu)- and (LMent,SC,SRu)-[Cp(PNMent)Ru(PPh3)Cl] with piperidine or morpholine in the presence of NH4PF6 led to the chiral-at-metal diastereomers (LMent,SC,RRu)- and (LMent,SC,SRu)-[Cp(PNMent)Ru(PPh3)NH3]PF6 (6% de).  相似文献   

8.
Three Cd(II) macroacyclic Schiff base complexes [CdL4(NO3)2] (4), [CdL5(NO3)2] (5), [CdL6(NO3)2] (6) were prepared by template condensation of 2-pyridinecarboxaldehyde with N1-(2-nitrobenzyl)-N1-(2-aminoethyl)ethane-1,2-diamine (L1), N1-(2-nitrobenzyl)-N1-(2-aminoethyl)propane-1,3-diamine (L2) or N1-(2-nitrobenzyl)-N1-(3-aminopropyl)propane-1,3-diamine (L3), in the presence of cadmium metal ion, respectively. Three Cd(II) complexes with L1, L2 and L3 were also synthesized. All complexes have been studied with IR, 1H NMR, 13C NMR, DEPT, COSY, HMQC and microanalysis. Two of these complexes, [CdL4(NO3)2] (4) and [CdL1(NO3)2] (1) have been characterized through X-ray crystallography. In complex 4, the Cd is in a six-coordinate environment comprised of the ligand N4-donor set and two oxygen atoms of two nitrate groups. In the polyamine complexes (1, 2 and 3) Cd and ligand are in a ratio of 1:1. Supporting ab initio HF-MO calculations have been undertaken using the standard 3-21G and 6-31G basis sets.  相似文献   

9.
Two new potentially octadentate N2O6 Schiff-base ligands 2-((E)-(2-(2-(2-((E)-2-hydroxy-3-methoxybenzylideneamino)phenoxy)phenoxy)phenylimino)methyl)-6-methoxyphenol H2L1 and 2-((E)-(2-(2-(2-((E)-2-hydroxy-3-methoxybenzylideneamino)phenoxy)-4-tert-butylphenoxy)phenylimino)methyl)-6-methoxyphenol H2L2 were prepared from the reaction of O-Vaniline with 1,2-bis(2′-aminophenoxy)benzene or 1,2-bis(2′-aminophenoxy)-4-t-butylbenzene, respectively. Reactions of H2L1 and H2L2 with copper(II) and zinc(II) salts in methanol in the presence of N(Et)3 gave neutral [CuL1]?·?0.5CH2Cl2, [CuL2], [ZnL1]?·?0.5CH2Cl2, and [ZnL2] complexes. The complexes were characterized by IR spectra, elemental analysis, magnetic susceptibility, ESI–MS spectra, molar conductance (Λm), UV-Vis spectra and, in the case of [ZnL1]?·?0.5CH2Cl2 and [ZnL2], with 1H- and 13C-NMR. The crystal structure of [ZnL1]?·?0.5CH2Cl2 has also been determined showing the metal ion in a highly distorted trigonal bipyramidal geometry. The electrochemical behavior of H2L2 and its Cu(II) complex, [CuL2], was studied and the formation constant of [CuL2] was evaluated using cyclic voltammetry. The logarithm value of formation constant of [CuL2] is 21.9.  相似文献   

10.
Compounds [Cu(L1)2] (1) and [Cu(L2)2] (2), where L1 and L2 are Schiff base ligands of 4-aminoantipyrine and substituted salicylaldehydes, were synthesized and characterized using various spectroscopic techniques such as elemental analysis, UV–Vis, IR, and NMR. The single crystal X-ray structures for L1, L2, and their corresponding Cu(II) complexes assembled in a 1:2 metal to ligand ratio were analyzed for their various weak H-bonding and dimeric association. The structural analysis of compounds 1 and 2, being the first crystal structures in this series, deserves special attention to help further the understanding in this area of structure–reactivity correlation studies. Further these compounds, composed of very similar chemical composition with a small difference in the substituent on the salicylaldehyde moiety, influenced through various weak inter- and intramolecular H-bonding and C–H?π interactions, rearrange the geometry around Cu(II) from a tetrahedrally distorted square planar geometry in [Cu(L1)2] (1) to square planar in [Cu(L2)2] (2). Steric strain imposed by the methyl substitution on the 4-aminoantipyrine moiety of the Schiff base ligand, causing this small change of the Cu(II) geometry, along with various weak interactions is analyzed in detail.  相似文献   

11.
New azido-bridged [MnIII(salabza)(μ-1,3-N3)]n (1), and [CuII4(salabza)2(μ-1,1-N3)2(N3)2(HOCH3)2],(2) complexes with an unsymmetrical Schiff base ligand, {H2salabza = N,N’-bis(salicylidene)-2-aminobenzylamine}, have been synthesized, characterized by spectroscopic and electrochemical methods, and their crystal structures have been determined by X-ray diffraction. In complex 1, each manganese(III) atom is coordinated with N2O2 donor atoms from salabza and two adjacent Mn(III) centers are linked by an end-to-end (EE) azide bridge to form a helical polymeric chain with octahedral geometry around the Mn(III) centers. Complex 2 is a centrosymmetric tetranuclear compound containing two types of Cu(II) centers with square pyramidal geometry. Each terminal copper atom is surrounded by N2O2 atoms of a salabza ligand, and the oxygen atom of the methanol molecule. Each central copper(II) ion is coordinated with two phenoxo oxygen atoms from one salabza, one terminal azido, and two end-on (EO) bridging azido ligands. The central copper(II) ions are linked to each other by the two end-on (EO) azido groups.  相似文献   

12.
Four tridentate O, N, O donor Schiff base ligands were prepared by the reaction of substituted benzhydrazide and appropriate salicylaldehyde. The complexes of these ligands were synthesized by refluxing the ligands with ruthenium(II) starting complexes of the formula [RuHCl(CO)(EPh3)2B] in benzene, where E = P or As; B = PPh3 or AsPh3 or pyridine. The newly synthesized complexes were characterized by elemental, spectral (FT‐IR, UV and NMR) and electrochemical data. On the basis of the above studies, an octahedral structure has been proposed for all the complexes. The catalytic efficiency of the complexes in aryl–aryl couplings and oxidation of alcohols was examined and their inhibition activity against the growth of the micro‐organisms was also examined. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

13.
Two nickel(II) complexes of [1 + 1] macrocyclic Schiff base ligand (L) have been prepared by cyclocondensation reactions between 1,3-diamino-2-propanol and 2-[3-(2-formylphenoxy)-2-hydroxypropoxy] benzaldehyde, using NiX2 (X = Br, and I) salts as template agents, and characterized by elemental analyses, IR, molar conductivity and electronic spectra in both solid and solution states. The single-crystal X-ray diffractions of the complexes are also reported that contain nickel(II) ion in a distorted octahedral geometry coordination of N2O3X (X = Br, I and NO3). In all complexes the ligand behaves as a pentadentate ligand. Cyclic voltammetric studies of nickel(II) complexes indicate a quasi-reversible redox wave in the negative potential range.  相似文献   

14.
Diorganotin(IV) complexes, [SnR2L] (1)-(4), (R = Me, Ph), of the terdentate Schiff bases N-[(2-pyrroyl)methylidene]-N′-tosylbenzene-1,2-diamine (H2L1) and N-[(2-hydroxyphenyl)metylidene]-N′-tosylbenzene-1,2-diamine (H2L2) have been synthesised. The complexes were obtained by addition of the appropriate ligand to a methanol suspension of the corresponding diorganotin(IV) dichloride in the presence of triethylamine. However, the reaction between the precursor [η5-C5H5Fe(CO)2]2SnCl2 and the Schiff bases in the presence of triethylamine gave (5) and (6), respectively. The crystal structures of the ligands and complexes have been studied by X-ray diffraction. The structure of [SnR2L] complexes shows the tin to be five-coordinate in a distorted square pyramidal environment with the dianionic ligand acting in a terdentate manner. In 5 and 6, the iron atom is in a slightly distorted octahedral environment and is meridionally coordinated by two ligands. Spectroscopic data for the ligands and complexes (IR, 1H, 13C and 119Sn NMR and mass spectra) are discussed and related to the structural information.  相似文献   

15.
The vibrational and 1H NMR data hints that the coordination of the 2,2′-dithiodipyridine (2-pySS) ligand to the [Ru(CN)5]3− metal center occurs through the sulfur atom instead of the nitrogen atoms which is usually observed for N-heterocyclic ligands. Electrochemical results show that this coordination mode implies an additional thermodynamic stabilization of the RuII over RuIII oxidation state due to a relative stronger π-back-bonding interaction with the empty low-lying dπ orbitals of the sulfur atom. Computational data reinforce the experimental results showing that the 2-pySS Lewis base centers are located on the sulfur atoms. Ligands containing only sulfur atoms as coordination sites (2,2′-dithiodipyridine N-oxide (2-pySSNO), 1,4-dithiane (1,4-dt), and 2,6-dithiaspiro[3.3]heptane (asp)) were also coordinated to the [Ru(CN)5]3− metal center to undoubtedly correlate the electrochemical results with the ligand coordination atom. Among the synthesized compounds, the [Ru(CN)5(1,4-dt)]3− and [Ru(CN)5(asp)]3− complexes showed to be able to form self-assembled monolayers (SAMs) on gold. These SAMs, which were characterized by SERS (surface-enhanced Raman scattering) spectroscopy, successfully assessed the heterogeneous electron transfer reaction of the cytochrome c metalloprotein in physiological medium.  相似文献   

16.
Schiff base mixed-ligand copper complexes [CuL1(phen)Cl2], [CuL1(bipy)Cl2], [Cu(L1)2Cl2], [Cu(L2)2Cl2], [CuL2(bipy)Cl2], and [CuL2(phen)Cl2] (where L1?=?4-[3,4-dimethoxy-benzylidene]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazole-3-one; L2?=?4-[3-hydroxy-4-nitro-benzylidene]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazole-3-one; phen?=?1,10-phenanthroline; and bipy?=?2,2′-bipyridine) have been synthesized and characterized. Their DNA-binding properties have been studied by electronic absorption spectra, viscosity, and electrochemical measurements. The absorption spectral and viscosity results suggest that the copper(II) complexes bind to DNA via partial intercalation. The addition of DNA resulting in the decrease of the peak current of the copper(II) complexes indicates their interaction. Interaction between the complexes and DNA has also been investigated by submarine gel electrophoresis. The copper complexes cleave supercoiled pUC19 DNA to nicked and linear forms through hydroxyl radical and singlet oxygen in the presence of 3-mercaptopropionic acid as the reducing agent. These copper complexes promote the photocleavage of pUC19 DNA under irradiation at 360?nm. Mechanistic study reveals that singlet oxygen is likely to be the reactive species responsible for the cleavage of plasmid DNA by the synthesized complexes. The in vitro antimicrobial study indicates that the metal chelates have higher activity against the bacterial and fungal strains than the free ligands.  相似文献   

17.
Treatment of [Ru(PPh3)3Cl2] with one equivalent of tridentate Schiff base 2-[(2-dimethylamino-ethylimino)-methyl]-phenol (HL) in the presence of triethylamine afforded a ruthenium(III) complex [RuCl3(κ2-N,N-NH2CH2CH2NMe2)(PPh3)] as a result of decomposition of HL. Interaction of HL and one equivalent of [RuHCl(CO)(PPh3)3], [Ru(CO)2Cl2] or [Ru(tht)4Cl2] (tht = tetrahydrothiophene) under different conditions led to isolation of the corresponding ruthenium(II) complexes [RuCl(κ3-N,N,O-L)(CO)(PPh3)] (2), [RuCl(κ3-N,N,O-L)(CO)2] (3), and a ruthenium(III) complex [RuCl2(κ3-N,N,O-L)(tht)] (4), respectively. Molecular structures of 1·CH2Cl2, 2·CH2Cl2, 3 and 4 have been determined by single-crystal X-ray diffraction.  相似文献   

18.
Cu(II) complexes of three bis(pyrrol-2-yl-methyleneamine) ligands were synthesized and characterized by elemental analyses, mass spectra, and IR spectra. X-ray diffraction analysis shows that [CuL3]2 is a dinuclear complex with an extremely distorted square-planar geometry. Furthermore, the antioxidant activities of the compounds have been investigated. The electrochemical properties of the Cu(II) complexes have also been studied by cyclic voltammetry. The Cu(II) complexes show similar superoxide dismutase (SOD) activity compared with that of the native Cu, Zn-SOD.  相似文献   

19.
Three new complexes, [(η6-C6H6)RuCl(C5H4N-2-CH=N-Ar)]PF6 (Ar = phenylmethylene (1), (4-methoxyphenyl)methylene (2), and phenylhydrazone (3)), were prepared by reacting [(η6-C6H6)Ru(μ-Cl)Cl]2 with N,N′-bidentate ligands in a 1 : 2 ratio. Full characterization of the complexes was accomplished using 1H and 13C NMR, elemental and thermal analyses, UV–vis and IR spectroscopy and single crystal X-ray structures. Single crystal structures confirmed a pseudo-octahedral three-legged, piano-stool geometry around Ru(II), with the ligand coordinated to the ruthenium(II) through two N atoms. The cytotoxicity of the mononuclear complexes was established against three human cancer cell lines and selectivity was also tested against non-cancerous human epithelial kidney (HEK 293) cells. The compounds were selective toward the tumor cells in contrast to the known anti-cancer drug 5-fluoro uracil which was not selective between the tumor cells and non-tumor cells. All the compounds showed moderate activity against MCF7 (human breast adenocarcinoma), but showed low antiproliferative activity against Caco-2 and HepG2. Also, antimicrobial activities of the complexes were tested against a panel of antimicrobial-susceptible and -resistant Gram-negative and Gram-positive bacteria. Of special interest is the anti-mycobacterial activity of all three synthesized complexes against Mycobacterium smegmatis, and bactericidal activity against resistant Enterococcus faecalis and methicillin-resistant Staphylococcus aureus ATCC 43300.  相似文献   

20.
By condensation of amantadine and 4-methoxysalicylaldehyde a new Schiff base HL was synthesized. A mixture of HL and zinc(II) chloride in an alcoholic medium leads to [Zn(HL)2Cl2] (1). However, the same reactants gave another different complex (ZnL2) (2) in the presence of NaOH. The two complexes were characterized by IR, 1H NMR, elemental analysis, molar conductance, and single-crystal X-ray diffraction. X-ray diffraction analysis reveals that complex 1 crystallizes in the triclinic system, Pī space group; each asymmetric unit consists of one zinc(II), two HL, and two chlorides. The tetra coordination of central zinc is attained by two chlorides and two oxygens from the Schiff base, forming a distorted tetrahedral geometry. Complex 2 crystallizes in the monoclinic system, P21/c space group; each asymmetric unit consists of one zinc(II) and two L. The tetra coordination of central zinc is attained by two nitrogens and two oxygens from the Schiff base, forming a distorted tetrahedral geometry.  相似文献   

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