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1.
The complexes of 4-chloro-2-methoxybenzoic acid anion with Mn2+, Co2+, Ni2+, Cu2+ and Zn2+ were obtained as polycrystalline solids with general formula M(C8H6ClO3)2·nH2O and colours typical for M(II) ions (Mn – slightly pink, Co – pink, Ni – slightly green, Cu – turquoise and Zn – white). The results of elemental, thermal and spectral analyses suggest that compounds of Mn(II), Cu(II) and Zn(II) are tetrahydrates whereas those of Co(II) and Ni(II) are pentahydrates. The carboxylate groups in these complexes are monodentate. The hydrates of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) heated in air to 1273 K are dehydrated in one step in the range of 323–411 K and form anhydrous salts which next in the range of 433–1212 K are decomposed to the following oxides: Mn3O4, CoO, NiO and ZnO. The final products of decomposition of Cu(II) complex are CuO and Cu. The solubility value in water at 293 K for all complexes is in the order of 10–3 mol dm–3. The plots of χM vs. temperature of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) follow the Curie–Weiss law. The magnetic moment values of Mn2+, Co2+, Ni2+ and Cu2+ ions in these complexes were determined in the range of 76−303 K and they change from: 5.88–6.04 μB for Mn(C8H6ClO3)2·4H2O, 3.96–4.75 μB for Co(C8H6ClO3)2·5H2O, 2.32–3.02 μB for Ni(C8H6ClO3)2·5H2O and 1.77–1.94 μB for Cu(C8H6ClO3)2·4H2O.  相似文献   

2.
Four new complexes of 2,3,4-trimethoxybenzoic acid anion with manganese(II), cobalt(II), nickel(II) and copper(II) cations were synthesized, analysed and characterized by standard chemical and physical methods. 2,3,4-Trimethoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) are polycrystalline compounds with colours typical for M(II) ions. The carboxylate group in the anhydrous complexes of Mn(II), Co(II) and Ni(II) is monodentate and in that of Cu(II) monohydrate is bidentate bridging one. The anhydrous complexes of Mn(II), Co(II) and Ni(II) heated in air to 1273 K are stable up to 505–517 K. Next in the range of 505–1205 K they decompose to the following oxides: Mn3O4, CoO, NiO. The complex of Cu(II) is stable up to 390 K, and next in the range of 390–443 K it loses one molecule of water. The final product of its decomposition is CuO. The solubility in water at 293 K is of the order of 10–3 mol dm–3 for the Mn(II) complex and 10–4 mol dm–3 for Co(II), Ni(II) and Cu(II) complexes. The magnetic moment values of Mn2+, Co2+, Ni2+ and Cu2+ ions in 2,3,4-trimethoxybenzoates experimentally determined in the range of 77–300 K change from 5.64–6.57 μB (for Mn2+), 4.73–5.17 μB (for Co2+), 3.26–3.35 μB (for Ni2+) and 0.27–1.42 μB (for Cu2+). 2,3,4-Trimethoxybenzoates of Mn(II), Co(II) and Ni(II) follow the Curie–Weiss law, whereas that of Cu(II) forms a dimer.  相似文献   

3.
The molecular structures of the isatin Schiff bases of S-methyldithiocarbazate (Hisasme) and S-benzyldithiocarbazate (Hisasbz) have been determined by X-ray diffraction and their complexes of general formula [ML2n(solvate) [M = Co2+, Ni2+, Zn2+; L = anionic forms of Hisasme or Hisasbz; solvate = DMF, DMSO; n = 1, 2] and [Sn(L)Ph2Cl]·nMeOH (n = 0, 1) have been synthesized and characterized by a variety of physicochemical techniques and X-ray diffraction. The bis-ligand complexes, [Ni(isasbz)2]·2DMSO and [Co(isasme)2]·DMF have a six-coordinate, distorted octahedral geometry with the two uninegatively charged tridentate ONS ligands coordinated to the metal ions meridionally via the amide O-atoms, the azomethine nitrogen atoms and the thiolate sulfur atoms. By contrast, the crystal structure of [Zn(isasbz)2]·2DMF shows a four-coordinate distorted tetrahedral geometry with the two Schiff bases coordinated as NS bidentate ligands via the azomethine nitrogen atoms and the thiolate sulfur atoms. Steric constraints of the rigid tridentate ligands lead to unusual ‘pseudo-coordination’ of the O-donors which occupy sites close to the metal but too distant to be considered as true coordinate bonds.The crystal structures of the tin(IV) complexes [SnLPh2Cl]·nMeOH (L = isasme and isasbz; n = 0, 1) also show that the Schiff bases act as monoanionic bidentate NS chelating agents coordinating the tin(IV) ion via the azomethine nitrogen atoms and the thiolate sulfur atoms, the tin atom in each complex is five-coordinate with a highly distorted geometry intermediate of square pyramidal and trigonal bipyramidal. Again Sn?O contacts are weak and do not qualify as coordinate bonds.  相似文献   

4.
New bi- and trihomonuclear Mn(II), Co(II), Ni(II), and Zn(II) complexes with sulfa-guanidine Schiff bases have been synthesized for potential chemotherapeutic use. The complexes are characterized using elemental and thermal (TGA) analyses, mass spectra (MS), molar conductance, IR, 1H-NMR, UV-Vis, and electron spin resonance (ESR) spectra as well as magnetic moment measurements. The low molar conductance values denote non-electrolytes. The thermal behavior of these chelates shows that the hydrated complexes lose water of hydration in the first step followed by loss of coordinated water followed immediately by decomposition of the anions and ligands in subsequent steps. IR and 1H-NMR data reveal that ligands are coordinated to the metal ions by two or three bidentate centers via the enol form of the carbonyl C=O group, enolic sulfonamide S(O)OH, and the nitrogen of azomethine. The UV-Vis and ESR spectra as well as magnetic moment data reveal that formation of octahedral [Mn2L1(AcO)2(H2O)6] (1), [Co2(L1)2(H2O)8] (2), [Ni2L1(AcO)2(H2O)6] (3), [Mn3L2(AcO)3(H2O)9] (5), [Co3L2(AcO)3(H2O)9] · 4H2O (6), [Ni3L2(AcO)3(H2O)9] · 7H2O (7), [Mn3L3(AcO)3(H2O)6] (9), [Co2(HL3)2(H2O)8] · 4H2O (10), [Ni3L3(AcO)3(H2O)9] (11), [Mn3L4(AcO)3(H2O)9] · H2O (13), [Co2(HL4)2(H2O)8] · 5H2O (14), and [Ni3L4(AcO)3(H2O)9] (15) while [Zn2L1(AcO)2(H2O)2] (4), [Zn3L2(AcO)3(H2O)3] · 2H2O (8), [Zn3L3(AcO)3(H2O)3] · 3H2O (12), and [Zn3L4(AcO)3(H2O)3] · 2H2O (16) are tetrahedral. The electron spray ionization (ESI) MS of the complexes showed isotope ion peaks of [M]+ and fragments supporting the formulation.  相似文献   

5.
Three novel paramagnetic metal complexes (MH2ID) of Ni2+, Cu2+ and VO2+ ions with 3‐hydroxy‐3,3’‐biindoline‐2,2’‐dione (dihydroindolone, H4ID) were synthesized and characterized by different spectroscopic methods. The ligand (H4ID) was synthesized via homocoupling reaction of isatin in presence of phenylalanine in methanol. Complexation of low valent Ni2+, Cu2+ ions and high valent VO2+ ions with H4ID carried out in 1: 2 molar ratios. A comparison in the catalytic potential of paramagnetic complexes of low and high valent metal ion was explored in the oxidation processes of cis‐cyclooctene, benzyl alcohol and thiophene by an aqueous H2O2, as a green terminal oxidant, in the presence and absence of acetonitrile, as an organic solvent, at 85 °C. NiH2ID, CuH2ID and VOH2ID show good catalytic activity, i.e. good chemo‐ and regioselectivity. VOH2ID has the highest catalytic potential compared to both Ni2+‐ and Cu2+‐species in the same homogenous aerobic atmosphere. Catalytic oxidation of other alkenes and alcohols was also studied using NiH2ID, CuH2ID or VOH2ID as a pre‐catalyst by an aqueous H2O2. A mechanistic pathway for those oxidation processes was proposed.  相似文献   

6.
Complexes of general formula, [M(isa-sme)2] · n(solvate) [M = Ni2+, Cu2+, Zn2+, Cd2+; isa-sme = monoanionic form of the Schiff base formed by condensation of isatin with S-methyldithiocarbazate; n = 1 or 1.5; solvate = MeCN, DMSO, MeOH or H2O] have been synthesized and characterized by a variety of physicochemical techniques. An X-ray crystallographic structure determination of the [Ni(isa-sme)2] · MeCN complex reveals a six-coordinate, distorted octahedral geometry. The two uninegatively charged, tridentate, Schiff base ligands are coordinated to the nickel(II) ion meridionally via the amide O-atoms, the azomethine N-atoms and the thiolate S-atoms. By contrast, the crystal structure of [Zn(isa-sme)2] · MeOH shows a four-coordinate distorted tetrahedral geometry. The two dithiocarbazate ligands are coordinated as NS bidentate chelates with the amide O-atom not coordinated. The structure of the copper(II) complex [Cu(isa-sme)2] · DMSO is complicated and comprises two different complexes in the asymmetric unit, one four- and the other five-coordinate. The four-coordinate copper(II) has a distorted (flattened) tetrahedral geometry as seen in the Zn(II) analogue whereas the five-coordinate copper(II) has a distorted square-pyramidal geometry with one ligand coordinated to the copper(II) ion as a tridentate (NSO) ligand and the other coordinated as a bidentate NS chelate. EPR spectroscopy indicates that in solution only one form is present, that being a distorted tetrahedral complex.  相似文献   

7.
Complexes of N-phthaloylglycinate (N-phthgly) and CoII, NiII, CuII, ZnII and CdII containing imidazole (imi), N-methylimidazole (mimi), 2,2-bipyridyl (bipy) and 1,10-phenanthroline (phen), and tridentate amines such as 2,2,2-terpyridine (terpy) and 2,4,6-(2-pyridyl)s-triazine (tptz), were prepared and characterized by conventional methods, i.r. spectra and by thermogravimetric analysis. For imi and mimi ternary complexes, the general formula [M(imi/mimi)2(N-phthgly)2nH2O, where M = CoII, NiII, CuII and ZnII applies. For CdII ternary complexes with imi, [Cd(imi)3(N-phthgly)2]·2H2O applies. For the bi and tridentate ligands, ternary complexes of the formula [M(L)(N-phthgly)2nH2O were obtained, where M = CoII, NiII, CuII and ZnII; L = bipy, phen, tptz and terpy. In all complexes, N-phthgly acts as a monodentate ligand, coordinating metal ions through the carboxylate oxygen, except for the ternary complexes of CoII, NiII and CuII with mimi and CuII and ZnII with imi, where the N-phthgly acts as a bidentate ligand, coordinating the metal ions through both carboxylate oxygen atoms.  相似文献   

8.
Synthesis of four different types of ligands Ar[COC(NOH)R] n (Ar = biphenyl, n = 1, HL1; Ar = biphenyl, n = 2, H2L2; Ar = diphenylmethane, n = 1, HL3; Ar = diphenylmethane, n = 2, H2L4; R = furfurylamine in all ligands) and their dinuclear Co2+, Ni2+, Cu2+, and Zn2+ complexes is reported herein. These compounds were characterized by elemental analysis, ICP-OES, FT-IR spectra, and magnetic susceptibility measurements. The ligands were further characterized by 1H NMR. The results suggest that dinuclear complexes of HL1 and HL3 have a metal to ligand mole ratio of 2: 2 and dinuclear complexes H2L2 and H2L4 have a metal to ligand mole ratio of 2: 1. Square pyramidal or octahedral structures are proposed for complexes of oxime ligands. Furthermore, extraction abilities of the four ligands were also evaluated in chloroform using selected transition metal picrates such as Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Pb2+. The ligands show strong binding ability towards Hg2+ and Cu2+ ions.  相似文献   

9.
Physico-chemical properties of 4-chloro-2-nitrobenzoates of Co(II), Ni(II), and Cu(II) were studied. The complexes were obtained as mono- and trihydrates with a metal ion to ligand ratio of 1:2. All analysed 4-chloro-2-nitrobenzoates are polycrystalline compounds with colours depending on the central ions: pink for Co(II), green for Ni(II), and blue for Cu(II) complexes. Their thermal decomposition was studied only in the range of 293–523 K, because it was found that on heating in air above 523 K 4-chloro-2-nitrobenzoates decompose explosively. Hydrated complexes lose crystallization water molecules in one step and anhydrous compounds are formed. The final products of their decomposition are the oxides of the respective transition metals. From the results it appears that during dehydration process no transformation of nitro group to nitrite takes place. The solubilities of analysed complexes in water at 293 K are of the order of 10–4–10–2 mol dm–3. The magnetic moment values of Co2+, Ni2+ and Cu2+ ions in 4-chloro-2-nitrobenzoates experimentally determined at 76–303 K change from 3.89 to 4.82 μB for Co(II) complex, from 2.25 to 2.98 μB for Ni(II) 4-chloro-2-nitrobenzoate, and from 0.27 to 1.44 μB for Cu(II) complex. 4-chloro-2-nitrobenzoates of Co(II), and Ni(II) follow the Curie–Weiss law. Complex of Cu(II) forms dimer.  相似文献   

10.
Guo  Yan-He  Ge  Qing-Chun  Lin  Hua-Kuan  Zhu  Shou-Rong  Lin  Hai 《Transition Metal Chemistry》2004,29(1):42-45
The coordination properties of two C3-symmetry hexaza tripods, 1,3,5-tri(2,5-diazahexyl)benzene (L1) and 1,3,5-tri(2,5-diazaheptyl)benzene (L2), towards Zn2+, Cu2+, Ni2+ and Co2+ ions, studied by potentiometric techniques, are reported. Both ligands form quite stable complexes either in a 1:1 or 1:3 M:L stoichiometry, presenting a preferential coordination order: Zn2+ < Cu2+ > Ni2+ > Co2+. It is observed that the different configurations of metal complexes are achieved due to the fact that tripodal ligands are flexible and not constrained into a rigid geometry.  相似文献   

11.
Summary Several new complexes of the title ligand (H2MPTS) with CoII, NiII, CuII, and CdII have been prepared. Structural assignments of the complexes have been made based on elemental analysis, molar conductivity, magnetic moment and spectral (i.r.,1H n.m.r., reflectance) studies. The compounds are non-conductors in dimethylsulphoxide. The neutral molecule is coordinated to the metal(II) sulphate as a bidentate ligandvia the two carbonyl groups. The ligand reacts with the metal(II) chlorides with the liberation of two hydrogen ions, behaving as a bianionic quadridentate (NONO) donor. Enolization is confirmed by the pH-titration of H2 MPTS and its metal(II) complexes against NaOH. A distorted octahedral structure is proposed for the CuII complex, while a square planar structure is suggested for both CoII and NiII complexes. The stoichiometry of the complexes formed in EtOH and buffer solutions, their apparent formation constants and the ranges for obedience to Beer's law are reported for CoII, NiII and CuII ions. The ligand pK values are calculated. The antimicrobial activity of H2 MPTS and its CoII, NiII, CuII and MnII complexes is demonstrated.  相似文献   

12.
CoII, NiII, CuII, ZnII and CdII complexes of N,N-bis(2-{[(2-methyl-2-phenyl-1,3-dioxolan-4-yl)methyl]amino}butyl)N′,N′-dihydroxyethanediimidamide (LH2) were synthesized and characterized by elemental analyses, IR, 1H- and 13C-NMR spectra, electronic spectra, magnetic susceptibility measurements, conductivity measurements and thermogravimetric analyses (TGA). The CoII, NiII and CuII complexes of LH2 were synthesized with 1?:?2 metal ligand stoichiometry. ZnII and CdII complexes with LH2 have a metal ligand ratio of 1?:?1. The reaction of LH2 with CoII, NiII, CuII, ZnII and CdII chloride give complexes Ni(LH)2, Cu(LH)2, Zn(LH2)(Cl)2, Cd(LH2)(Cl)2, respectively.  相似文献   

13.
A bioactive Schiff base HL i.e. 2‐hydroxy‐benzoic acid(3,4‐dihydro‐2H ‐naphthalen‐1‐ylidene)‐hydrazide was synthesized by reacting equimolar amount of salicylic acid hydrazide and 1‐tetralone. Co(II), Ni(II) and Zn(II) complexes of ligand HL was synthesized in 1:1 and 1:2 molar ratio of metal to ligand. The structure of the synthesized ligand and metal complexes was established by elemental analysis, molar conductance, magnetic susceptibility measurements, electronic, IR and EPR spectral techniques. For determining the thermal stability the TGA has been done. In DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6–31 + g(d,p) basis set. Spectral data reveal that ligand behave uninegative tridentate in ML complexes and uninegative bidentate in ML2 complexes. On the basis of characterization octahedral geometry has been assigned for Co(II) and Ni(II) complexes, while tetrahedral for Zn(II) complexes. Antibacterial activity of the synthesized compounds were evaluated against Staphylococcus aureus , Bacillus subtilis, Escherichia coli , Xanthomonas campestris and Pseudomonas aeruginosa and the results revealed that metal complexes show enhanced activity in comparison to free ligand.  相似文献   

14.
New metal based triazoles (1–12) have been synthesized by the interaction of novel Schiff base ligands (L1–L3) with the Co(II), Ni(II), Cu(II) and Zn(II) metal ions. The Schiff base ligands and their all metal(II) complexes have been thoroughly characterized using various physical, analytical and spectroscopic techniques. In vitro bacterial and fungal inhibition studies were carried out to examine the antibacterial and antifungal profile of the Schiff bases in comparison to their metal(II) complexes against two Gram‐positive, four Gram‐negative and six fungal strains. The bioactivity data showed the metal(II) complexes to have more potent antibacterial and antifungal activity than their uncomplexed parent Schiff bases against one or more bacterial and fungal species. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

15.
Summary Reaction of one mole of acetylacetone with two moles of 4-phenylthiosemicarbazide yields the unusual Schiff base, MeC(=N-NHCSNHPh)CH2C(=NNHCSNHPh)Me. APT = H2L) acetylacetone bis(4-phenylthiosemicarbazone). The complexes of CoII, NiII, CuII, ZnII and UVIO2 have been prepared and characterized by analytical, i.r., electronic spectral and magnetic measurements. The CoII, NiII and CuII complexes have been assigned square-planar stereochemistry on the basis of magnetic and spectroscopic studies. The ligand is a neutral or dibasic quadridentate SNNS donor as revealed by i.r. spectral studies.  相似文献   

16.
Herein, we report the synthesis of eight new mononuclear and binuclear Co2+, Ni2+, Cu2+, and Zn2+ methoxy thiosemicarbazone (MTSC) complexes aiming at obtaining thiosemicarbazone complex with potent biological activity. The structure of the MTSC ligand and its metal complexes was fully characterized by elemental analysis, spectroscopic techniques (NMR, FTIR, UV-Vis), molar conductivity, thermogravimetric analysis (TG), and thermal differential analysis (DrTGA). The spectral and analytical data revealed that the obtained thiosemicarbazone-metal complexes have octahedral geometry around the metal center, except for the Zn2+-thiosemicarbazone complexes, which showed a tetrahedral geometry. The antibacterial and antifungal activities of the MTSC ligand and its (Co2+, Ni2+, Cu2+, and Zn2+) metal complexes were also investigated. Interestingly, the antibacterial activity of MTSC- metal complexes against examined bacteria was higher than that of the MTSC alone, which indicates that metal complexation improved the antibacterial activity of the parent ligand. Among different metal complexes, the MTSC- mono- and binuclear Cu2+ complexes showed significant antibacterial activity against Bacillus subtilis and Proteus vulgaris, better than that of the standard gentamycin drug. The in silico molecular docking study has revealed that the MTSC ligand could be a potential inhibitor for the oxidoreductase protein.  相似文献   

17.
Interactions of nanofilms containing ethanolamino groups with cobalt(II), nickel(II), copper(II), and zinc(II) ammoniates at the surface of polyvinylchloride plates and with chromium(III) ammoniate in a solution of ammonium chloride were studied. It was found that the groups of the film, together with chloride ions, displace all ammonia molecules from the inner coordination sphere of the metal. The average number of the ethanolamino N atoms of the film participating in formation of the metal ion coordination sphere is 3.35, 3.47, 3.67, 3.42, and 3.37 for Co2+, Ni2+, Cu2+, Zn2+, and Cr3+ complexes, respectively. The average number of chloride ions is 2 for Co2+, Ni2+, Cu2+, and Zn2+ and 3 for Cr3+. The coordination number of the central atoms is 6. The Cr3+ ion forms a coordination sphere composed of three N atoms and three chloride ions and a coordination sphere (charged 1+) made up of four N atoms and two chloride ions, with the third chloride ion being in the outer sphere. The Co2+, Ni2+, and Cu2+ ions form uncharged coordination spheres of two types: (1) with four N atoms and two chloride ions and (2) with three N atoms, two chloride ions, and the O atom of the ethanol hydroxyl group.  相似文献   

18.
A new, simple Cu2+ nano‐structure Schiff base complex in methanol medium has been synthesized by the ultrasonic method. Structure of the compound was confirmed by FT‐IR, GC‐Mass and other spectroscopic techniques. The copper oxide (CuO) was achieved from the copper nano‐structure Schiff base complex as the raw material after calcination for 3 hr at 600 °C. According to results Cu2+ gives a complex with mole ratio 1:2 of metal to ligand (ML2) with Schiff base which a distorted square planer is the most probable geometry for it. The calculations results from XRD patterns propose the nano‐sized complexes. The SEM images show morphology of both the copper complex and the CuO powder were plate‐like. The metal chelates of Cu2+ in two states of bulk and nano have been screened for their in vitro antibacterial activity against four bacteria, gram‐positive (Staphylococcus aureus) and gram‐negative (Escherichia coli) and three strains of fungus (Aspergillus flavus). The nano metal chelates were shown to possess more antibacterial activity than the bulk chelate. Finally, the empirical parameters of Schiff base compounds showed a good agreement with theoretical ones.  相似文献   

19.
New Schiff bases, N,N′-bis(salicylidene)-4-aminobenzylamine (H2L1), N,N′-bis(3-methoxysalicylidene)-4-aminobenzylamine (H2L2), and N,N′-bis(4-hydroxysalicylidene)-4-aminobenzylamine (H2L3), with their nickel(II), cobalt(II), and copper(II) complexes have been synthesized and characterized by elemental analyses, electronic absorption, FT-IR, magnetic susceptibility, and conductance measurements. For the ligands, 1H and 13C NMR and mass spectra were obtained. The tetradentate ligands coordinate to the metal ions through the phenolic oxygen and azomethine nitrogens. The keto-enol tautomeric forms of the Schiff bases H2L1, H2L2, and H2L3 have been investigated in polar and apolar solvents. All compounds were non-electrolytes in DMSO (~10?3 M) according to the conductance measurements. Antimicrobial activities of the Schiff bases and their complexes have been tested against Acinobacter baumannii, Pseudomonas aeruginosa, Micrococcus luteus, Bacillus megaterium, Corynebacterium xerosis, Staphylococcus aureus, Escherichia coli, Candida albicans, Rhodotorula rubra, and Kluyveromyces marxianus by the disc diffusion method; biological activity increases on complexation.  相似文献   

20.
Summary Complexes of CoII, NiII, CuII, ZnII, CdII, HgII and UO 2 II with benzil bis(4-phenylthiosemicarbazone), H2BPT, have been synthesized and their structures assigned based on elemental analysis, molar conductivity, magnetic susceptibility and spectroscopic measurements. The i.r. spectra suggest that the ligand behaves as a binegative quadridentate (NSSN) (CoII, CuII, HgII and UO 2 II complexes) or as a binegative quadridentate-neutral bidentate chelating agent (NiII, ZnII and CdII complexes). Octahedral structures for the CoII and NiII complexes and square-planar structure for the CuII complex are suggested on the basis of magnetic and spectral evidence. The crystal field parameters (Dq, B and B) for the CoII complex are calculated and agree fairly well with the values reported for known octahedral complexes. The ligand can be used for the microdetermination of NiII ions of concentration in the 0.4–6×10–4 mol l–1 range and the apparent formation constant for the species generated in solution has also been calculated.  相似文献   

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