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1.
The reaction of α-benzoinoxime, H2BNO with FeCl3 in the presence of Et3N as a base gives the mononuclear Fe(III) complex, Fe(HBNO)3 (1). Treatment of 1 with a methanolic solution of KOH at room temperature leads to a dinuclear Fe(III)–Fe(III) complex, [Fe(HBNO)2OH]2 (2). The complexes were initially characterized on the basis of their elemental, mass and thermal analyses. The IR studies were useful in assigning the coordination mode of the benzoinoxime ligand to the iron metal. In addition, the presence of a hydroxo-bridge in the dimeric complex 2 is inferred from the IR spectral studies. Room-temperature Mössbauer studies indicated octahedral, high-spin iron(III). Variable-temperature magnetic susceptibility measurements supported the existence of the μ-dihydroxo-bridging structure core, FeIII(μ-OH)2FeIII in the dinuclear complex 2. Theoretical modelling of the magnetic data indicated a weak antiferromagnetic spin exchange between the iron(III) centers (J = −8.35 cm−1, g = 2.01, ρ = 0.02 and TIP = 1.7 × 10−4 cm3 mol−1 for H = −2JS1 · S2). The electronic spectra of the complexes revealed two bands due to d–d transitions and one band assignable to an oxygen (pπ) → Fe(dπ∗) LMCT transition observed in each complex. An additional charge-transfer transition, assignable to μ-hydroxo(pπ) → Fe(dπ∗), was observed for the dimeric complex 2. The structural and vibrational behaviors of these complexes have been elucidated with quantum mechanical methods.  相似文献   

2.
Three new μ‐oxamido‐bridged heterodinuclear copper (II)‐chromium (III) complexes formulated [Cu(Me2oxpn)Cr‐(L)2](NO3)3, where Me2oxpn denotes N,N'‐bis(3‐amino‐2, 2‐dimethylpropyl)oxamido dianion and L represents 5‐methyl‐1,10‐phenanthroline (Mephen), 4,7‐diphenyl‐1,10‐phenanthroline (Ph2phen) or 2,2′‐bipyridine (bpy), have been synthesized and characterized by elemental analyses, IR and electronic spectral studies, magnetic moments of room‐temperature and molar conductivity measurements. It is proposed that these complexes have oxamido‐bridged structures consisting of planar copper (II) and octahedral chromium (III) ions. The variable temperature magnetic susceptibilities (4.2–300 K) of complexes [Cu(Me2oxpn)Cr(Ph2phen)2](NO3)3 (1) and [Cu(Me2oxpn)Cr(Mephen)2] (NO3)3 (2) were further measured and studied, demonstrating the ferromagnetic interaction between the adjacent chromium (III) and copper (II) ions through the oxamido‐bridge in both complexes 1 and 2. Based on the spin Hamiltonian, ? = ‐ 2J?1 · ?2, the exchange integrals J were evaluated as + 21.5 an?1 for 1 and + 22.8 cm?1 for 2.  相似文献   

3.
Summary Three Cr(III) species (dichlorotetraaquachromium (III), [CrCl2(H2O)4]+; monochloropentaaquachromium(III), [CrCl(H2O)5]2+; and hexaaquachromium(III), [Cr(H2O)6]3+) have been separated and determined by capillary electrophoresis. The first two complexes could be detected in direct mode in phosphate buffer, but because the absorption of complex [Cr(H2O)6]3+ is poor in the UV range, indirect UV detection had to be used. For indirect detection 5 mM imidazole was added to the buffer solution. The formation and decomposition of the different Cr(III) complexes were monitored in time after the preparation of solutions of CrCl3.6H2O. The slowest process was the decomposition of [CrCl(H2O)5]2+; 300 h after preparation of a solution of CrCl3.6H2O of pH 1 the solution contained only [Cr(H2O)6]3+. The effects of pH and the content of some matrix ions on the rates of conversion of the complexes were studied. The kinetic characteristics of this complex system could be investigated adequately by means of capillary electrophoresis. Presented at Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 1–3, 1999  相似文献   

4.
Monomeric and Dimeric Chromium(III) Phthalocyanines: Synthesis and Properties of Hydroxopyridinophthalocyaninatochromium(III) and μ-Oxodi(pyridinophthalocyaninatochromium(III)) Heating of ?[Cr(OH)Pc2?]”? in pyridine (Py) gives the paramagnetic (T = 273 K) complexes [Cr(OH)(Py)Pc2?] (μCr = 3.84 μB) and [(Cr(Py)Pc2?)2O] (μCr = 1.24 μB) by consecutive substitution and condensation reactions. The UV-VIS spectra are characterized by the typical B, Q, and N regions of the Pc2? ligand being shifted hypsochromically for the dimer with respect to the monomer due to excitonic coupling (1.5 kK). Regions of weak absorbance between 8 and 13 resp. 19 kK are assigned to trip-quartet transitions for both complexes. A weak band at 870 cm?1 in the FIR/MIR spectra is assigned to vas(Cr? O? Cr). In the resonance Raman(RR) spectra v(Cr? O) at 514 cm?1 resp. vs(Cr? O? Cr) at 426 cm?1 is selectively enhanced. Further strong RR-lines of the μ-Oxo dimer at 110 and 631 cm?1 are assigned to a (Py? Cr? O)- resp. internal pyridine deformation of a1g symmetry. An assignment as 2vas(Cr? O? Cr) is proposed for the remarkable RR line at 1740 cm?1.  相似文献   

5.
The reactions of Ga(acac)3 with salicylaldoxime (saoH2) and methyl-salicylaldoxime (Me-saoH2) in dichloromethane/hexane afforded the complexes [Ga(acac)(saoH)2] (1) and [Ga(acac)3][Ga(acac)(MesaoH)2] (2), respectively, in high yields. The crystal structures of 1 and 2 have been determined by single-crystal X-ray crystallography. Both complexes are mononuclear with the Ga(III) atoms being in octahedral environments surrounded by two bidentate chelate R-saoH and one bidentate chelate acac ligands. A [Ga(acac)3] moiety has co-crystallized along with the methylsalicylaldoximato complex. Characteristic IR as well as NMR data are discussed in terms of the nature of bonding in the structures of the two complexes. 1H and 13C NMR data in CDCl3 indicate that the salicylaldoximato complexes isomerize in solution.  相似文献   

6.
Two polydentade Schiff base ligands and their Ru(III), Cr(III) and Fe(III) complexes were synthesized and characterized by elemental analysis (C, H, N), UV/Vis, FT IR, 1H and 13C NMR, LC–MS/MS, molar conductivity and magnetic susceptibility techniques. The absorption bands in the electronic spectra and magnetic moment measurements verified an octahedral environment around the metal ions in the complexes. The thermal stabilities were investigated using TGA. The synthesized complexes were used in the catalytic oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1,4-naphthoquinone; vitamin K3, menadione, 2MNQ; using hydrogen peroxide, acetic acid and sulfuric acid. L1-Fe(III) complex showed very efficient catalytic activity with 58.54% selectivity in the conversions of 79.11%.  相似文献   

7.
Polymer coordinated chromium(III) complexes [Cr(bpy)2(PAA)2]+, 1 , [Cr(bpy)2-(PMA)2]+, 2 , [Cr(phen)2(PAA)2]+, 3 , and [Cr(phen)2(PMA)2]+, 4 , [where bpy, phen, PAA and PMA are, respectively, 2,2′-bipyridine, 1,10-phenanthroline, poly(acrylic acid), and poly(methacrylic acid)] were synthesized. The polymer–chromium(III) complexes were characterized by elemental and spectroscopic analyses. Thermal substitution reactions of these macromolecular chromium(III) complexes in basic solutions lead to the replacement of the polypyridyl ligand by hydroxide ion while in strong acidic solutions the polymer complexes precipitate out. The photochemical reactions are qualitatively similar to that of the thermal reactions and the quantum yields are dependant on the pH of the medium. Further, lower quantum yields were observed for the aquation of the polymer complexes in comparison with the monomeric chromium(III) complexes and the results are discussed in terms of the effect of the polymer environment. Flash photolysis of 1 and 3 results in the formation of transients with maxima at 480 nm for 1 and 470 nm, 580 nm for 3 . The decay of the transients were found to obey first order kinetics and the rate constants were determined. The transients were suggested to be the alkyl-chromium complexes. Flash photolysis of 2 and 4 does not produce transients which is interpreted to be due to the presence of a methyl group in the ligand which hinders the formation of the carbonchromium bond.  相似文献   

8.
Low‐coordinate organoCr(III) complexes supported by the silylamido ligand –N(SiMe3)DIPP (DIPP = 2,6‐diisopropylphenyl) are ethylene polymerization catalyst precursors without the need of additional cocatalyst. The reaction of CrCl3(THF)3 with 3 or 2 equiv. of LiN(SiMe3)DIPP yields either a four‐membered cyclometalated Cr complex or Cr[N(SiMe3)DIPP]2Cl, respectively, with no trace of Cr[N(SiMe3)DIPP]3. Addition of 1 equiv. of LiN(SiMe3)DIPP to Cr[N(SiMe3)DIPP]2Cl also leads to the four‐membered metallacycle, which upon heating transforms to a new six‐membered Cr metallacycle, likely via a σ‐bond metathesis step. Cr[N(SiMe3)DIPP]2Cl can be readily converted to bis(amido)Cr(III) vinyl and alkyl complexes Cr[N(SiMe3)DIPP]2R (R = vinyl, Bn, and Me). All of these structurally characterized low‐coordinate Cr(III) complexes with a Cr–C bond initiate the polymerization of ethylene in the absence of activators or cocatalysts, producing ultra‐high‐molecular weight polyethylene.  相似文献   

9.
Terbium(III) and dysprosium(III) nitrate complexes with variously substituted 2,6-diphenylpiperidin-4-ones (L1)-(L10) of general formula [Ln(L)(NO3)2(H2O)2]NO3 have been synthesized. These complexes have been characterized by analytical, spectral and thermal studies. Molar conductance data show that these complexes are 1:1 electrolytes. The presence of two coordinated water molecules is confirmed by thermal and infrared spectral studies. IR spectral data indicate that piperidin-4-ones, in spite of having two coordinating sites, are monodentate, coordinating only through ring nitrogen. The IR and conductance data reveal the presence of two bidentate and one ionic nitrate groups. The nephelauxetic ratio (β), covalency factor (b1/2) and Sinha’s parameter (δ) evaluated from electronic spectral data of dysprosium(III) complexes indicate a little covalency in metal-ligand bonding.  相似文献   

10.
A platinum-lined, flowing autoclave facility is used to investigate the solubility behavior of Cr2O3 and FeCr2O4 in alkaline sodium phosphate, sodium hydroxide, and ammonium hydroxide solutions between 21 and 288°C. Baseline Cr(III) ion solubilities were found to be on the order of 0.1 nmolal, which were enhanced by the formation of anionic hydroxo and phosphato complexes. At temperatures below 51°C, the activity of Cr(III) ions in aqueous solution is controlled by a Cr(OH)3·3H2O solid phase rather than Cr2O3; above 51°C the saturating solid phase is -CrOOH. Measured chromium solubilities were interpreted via a Cr(III) ion hydrolysis/complexing model and thermodynamic functions for the hydrolysis/complexing reaction equilibria were obtained from least-squares analyses of the data. The existence of four new Cr(III) ion complexes is reported: Cr(OH)3(H2PO4), Cr(OH)3(HPO4)2–, Cr(OH)3(PO4)3–, and Cr(OH)4(HPO4)-(H2PO4)4–. The last species is the dominant Cr(III) ion complex in concentrated, alkaline phosphate solutions at elevated temperatures.  相似文献   

11.
In the current work, two triazine‐based multidentate ligands (H2L1 and H2L2) and their homo‐dinuclear Mn (II), mononuclear Ln (III) and hetero‐dinuclear Mn (II)/Ln (III) (Where Ln: Eu or La) complexes were synthesized and characterized by spectroscopic and analytical methods. Single crystals of a homo‐dinuclear Mn (II) complex {[Mn (HL1)(CH3OH)](ClO4·CH3OH}2 ( 1 ) were obtained and the molecular structure was determined by X‐ray diffraction method. In the structure of the complex, each Mn (II) ion is seven‐coordinate and one of the phenolic oxygen bridges two Mn (II) centre forming a dimeric structure. The UV–Vis. and photoluminescence properties of synthesized ligands and their metal complexes were investigated in DMF solution and the compounds showed emission bands in the UV–Vis. region. The catecholase enzyme‐like activity of the complexes were studied for 3,5‐DTBC → 3,5‐DTBQ conversion in the presence of air oxygen. Homo‐dinuclear Mn (II) complexes ( 1 and 4 ) were found to efficiently catalyse 3,5‐DTBC → 3,5‐DTBQ conversion with the turnover numbers of 37.25 and 35.78 h?1 (kcat), respectively. Mononuclear Eu (III) and La (III) complexes did not show catecholase activity.  相似文献   

12.
The reactions of Al(III), Ga(III) and In(III) nitrates with 2-quinaldic acid (qaH) afforded [Al2(OH)2(qa)4]·2H2O (1), [Ga(qa)2(H2O)2]NO3 (2) and [In(qa)2(NO3)(H2O)] (3), respectively, in high yields. The crystal structures of 1, 2 and 3 have been determined by single-crystal X-ray crystallography. The structure of 1 features a di-hydroxo bridged [Al2(μ-OH)2]4+ dimer in which each Al(III) is further ligated by two bidentate chelate qa? ligands. Complexes 2 and 3 are mononuclear with the M(III) ions in octahedral environments surrounded by two bidentate chelate qa? and two H2O in 2 or one H2O and a terminal NO3? in 3. Characteristic IR as well as thermal analysis and solid-state fluorescence are discussed.  相似文献   

13.
The preparation and some properties of the deprotonated complexes of oxamic acid with Au(III) and Rh(III) are reported. On the basis of analytical results, conductometric measurements, magnetic moments and spectral data (IR and UV-visible), a square planar structure is proposed for K[AuL(OH)2] and octahedral for K3[RhL 3] 3H2O (whereLH2=oxamic acid).L 2– acts as a bidentate, non-bridging ligand.
Komplexe der Oxamidsäure mit Au(III) und Rh(III)
Zusammenfassung Es wird über die Darstellung und einige Eigenschaften von deprotonierten Komplexen der Oxamidsäure mit Au(III) und Rh(III) berichtet. Auf der Grundlage von analytischen Ergebnissen, Leitfähigkeitsmessungen, magnetischen Momenten und IR- und UV(vis)-spektroskopischen Daten wird für K[AuL(OH)2] eine quadratisch planare und für K3[RhL 3] 3 H2O eine oktaedrische Struktur vorgeschlagen (LH2=Oxamidsäure).L 2– reagiert als zweizähniger, nicht überbrückender Ligand.
  相似文献   

14.
尹汉东  王传华  邢秋菊 《中国化学》2005,23(12):1631-1636
Three bismuth(Ⅲ) complexes Bi(1,10-phen)[S2CN(CH3)2]2(NO3) (1), {Bi(S2COCH3)[S2CNC6Hs(CH3)]2}2 (2) and [Bi(S2CNBu2)2(CH3OH)(NO3)]∞ (3) were synthesized and characterized by elemental analysis and IR spectra. Their crystal structures were determined by X-ray single crystal diffraction analysis. Studies show that complex 1 has a monomeric structure with the central bismuth atom eight-coordinated in a capped distorted pentagonal bipyramidal geometry. The complex 2 takes centrosymmetric dimeric structure and the bismuth atoms are seven-coordinated in distorted pentagonal bipyramidal geometry.In complex 3, the bismuth atoms are seven-coordinated in distorted pentagonal bipyramidal geometry by bridging nitrate O atoms and the resulting structure is onedimensional infinite chain polymer.  相似文献   

15.
Seven new μ‐oxamido copper(II)‐lanthanide(III) heterobimetalic complexes described by the formula Cu(obbz) Ln‐(Ph‐phen)2NO3(Ln = La, Nd, Eu, Gd, Tb, Ho, Er), where obbz denotes the oxamidobis(benzoato) and Ph‐phen represents 5‐phenyl‐1, 10‐phenanthroline, have been synthesized and characterized by the elemental analyses, spectroscopic (IR, UV, ESR) studies, magnetic moments (at room temperature) and molar conductivity measurement. The temperature dependence of the magnetic susceptibility of Cu(obbz)Gd(Ph‐phen)2NO3 complex has been measured over the range 4.2–300 K. The least‐squares fit of the experimental susceptibilities based on the spin Hamiltonian operator, ? = ?2 J?1·?2, yielded J= +1.28 cm?1, a weak ferromagnetic coupling, A plausible mechanism for a ferromagnetic coupling between Gd(III)‐Cu(II) is discussed in terms of spin‐polarization.  相似文献   

16.
A new hydroxo‐bridged dimeric Cr(III) complex [Cr(saltn)OH]2·4H2O [H2saltn=N,N′‐bis(salicylidene)trimethylenediamine] has been synthesized and its structural and magnetic properties have been investigated. The complex crystallizes in the triclinic space group P‐1 with one dimeric formula unit in a cell of dimensions a=0.95828(19) nm, b=0.95926(19) nm, c=1.0437(2) nm, α=86.77(3)°, β=82.48(3)°, and γ=64.93(3)°. The geometry around each chromium(III) center is six‐coordinate, distorted‐octahedral. The bridging Cr2O2 unit is strictly planar, as required by the crystallographic symmetry. The Cr? O? Cr′ bridging angle is 99.94(16)°, and the distance between Cr…Cr′ is 0.3019 nm. The magnetic susceptibility of the complex has been examined in the range of 2‐300 K. By using the spin‐spin coupled model for an S1=S2=3/2 dimeric system , the magnetic data were fitted to give the parameters of g=2.01(1), J=‐0.85(2) cm‐1, and zJ' =0.18(3)cm‐1, indicating the presence of a weak antiferromagnetic spin‐exchange interaction between the Cr(III) ions in the binuclear complex.  相似文献   

17.
A novel Schiff base ligand (H‐DPPMHQ) derived from 2‐hydrazineylquinoline and 1,3‐diphenyl‐1H‐pyrazole‐5‐carbaldehyde and its dimeric complexes with compositions [Cr(DPPMHQ)Cl]2?2Cl and [M(DPPMHQ)Cl]2 (where M = Cu(II), Co(II), Ni(II) and Zn(II)) have been synthesized and characterized using physicochemical methods like elemental analysis, magnetic susceptibility and molar conductivity measurements, multispectral techniques and electrochemical studies. The molar conductance data reveal that all metal chelates are non‐electrolytes, except the Cr(III) complex which shows a ΛM value of 146.82 Ω?1 cm2 mol?1, indicating that it is a 1:2 electrolyte. Infrared spectral results show that the metal is organized through four nitrogen atoms (azomethine and deprotonated imine groups, pyrazole and quinoline rings) besides chlorine atoms. The NH proton is also displaced during complexation, as indicated by 1H NMR spectral data. Based on the electron spin resonance and ligand field parameter data, the bonding parameters of these complexes have been calculated. Using Coats–Redfern and Horowitz–Metzger equations, thermodynamic parameters were determined. The spectral data indicate that the dimeric complexes have octahedral geometry around the central metal ions. The cytotoxic activities of all compounds were evaluated towards human breast cancer (MCF‐7) and lung cancer (A549) cell lines.  相似文献   

18.
Reactions of 2-(L-carboxyl-2-hydroxyphenyl)thiazolidine with different chromium(III) salts [CrCl3?·?6H2O, K3[Cr(SCN)6], NH4[Cr(NH3)2(SCN)4]?·?H2O, [Cr(urea)6]Cl3?·?3H2O and [Cr(CH3COO)2H2O]2] under varied reaction conditions afforded many new mixed-ligand chromium(III) complexes. The ligand is a tridentate dibasic NSO donor except for complexes 1 and 4 where two moles of the ligand are present for each molecule of complex, one functioning as a dibasic tridentate (NSO) and the other as a monobasic bidentate (NS) (phenolic OH and carboxylic COOH groups remaining uncoordinated). The complexes have been characterized by elemental analyses, magnetic susceptibilities, molar conductances, molecular weights and spectroscopic (IR, Uv-vis) data. The ligand field parameters and NSH Hamiltonian parameters suggest tetragonal geometries of the complexes.  相似文献   

19.
The properties of the iron(III) complexes of the ditopic macrocyclic ligand with three aminopropyl pendant arms, L1 = 3,7,11-tris-(3-aminopropyl)-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene were investigated in aqueous solution. Potentiometric studies indicated the presence of mononuclear [FeHhL1]h+3 (h = 0–3), and dinuclear [Fe2L1]6+, [Fe2L1(OH)]5+ and [Fe2L1(OH)2]4+ complexes, and their stability constants were determined at 298.2 K and ionic strength 0.10 mol dm−3 in KNO3. The log K values of mononuclear protonated species indicated the consecutive deprotonation of the aminopropyl arms, suggesting the nitrogen donor atoms from the macrocycle as the preferred coordination environment for the first metal centre, and the amines from the pendant arms for the second one. The dinuclear complex is formed at about 85% of the total amount of the metal ion for 2:1 Fe:L1 ratio solutions at pH 4.0–4.5. The log K values of the deprotonation of dinuclear hydrolysed species are consistent with the presence of two water molecules directly bound to the metal centres. Spectroscopic UV–Vis and IR data for 2:1 Fe3+:L1 ratio samples confirmed the existence of dinuclear and hydroxo dinuclear species. EPR spectra of these solutions were interpreted by an equilibrium of two high-spin d5 state of iron(III) species with different rhombic E/D distortions. Electrochemical studies also established the formation of mono- and dinuclear complexes, showing irreversible redox behaviour. The two metal centres on the dinuclear complexes have only weak interactions.  相似文献   

20.
Four μ- oxamido heterodinuclear complexes, [Cu (oxae) Cr (L)2 ] (NO3) 3, where oxae denotes the N, N'bis (2-aminoethyl) oxamido dianion and L represents 1,10-phenanthroline (phen); 5-nitro-1,10-phenanthroline (NO2-phen); 5-methyl-1, 10-phenanthroline (Me-phen) and 2, 2′-bipyridine (bpy), have been synthesized and characterized by elemental analyses, magnetic moments (at room temperature) and molar conductivity measurements and spectroscopy. It is proposed that these complexes have extended oxamido-bridged structures consisting of a copper (II) ion and a chromium (III) ion, which have a square planar environment and octahedral environment, respectively. The cryomagnetic properties of the [Cu(oxae)Cr(bpy)2(NO3)3(1) and [Cu(oxae)Cr(phen)2](NO3)3(2) complexes have been measured over the range of 4.2–300 K. The leastsquares fit of the experimental data based on the spin Hamiltonian, ? = - 2J?1·?2, the exchange integrals (J) were evaluated as +36.9 cm?1 for 1 and +35.8 cm?1 for 2. The reds have connived that the spin coupling between the adjacent copper (II) and chromium (III) ions through oxamido-bridge in both 1 and 2 is ferromagnetic.  相似文献   

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