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1.
On Reactions of oxygenated Cobalt(II) Complexes. V. Reactivity of diastereoisomeric μ-peroxo-μ-hydroxo-dicobalt(III) Ions The kinetics of dissociation of μ-peroxo-μ-hydroxo-dicobalt(III) chelates have been reinvestigated using a stopped flow technique. The binuclear cations [(trien)Co(O2, OH) Co(trien)]3+, [(tren)Co(O2, OH)Co(tren)]3+ and [(en)2Co(O2, OH)Co(en)2]3+ dissociate on acidifying to Co2+ and the protonated ligand and up to 100% of the bound O2 is evolved. The dissociation is H+-catalyzed and first order in complex. The observed rate constants at pH 2 are in the range of 10?3 to 10?1 s?1 (20°). They depend not only on the nature of the ligand and on ligand configuration but also on the diastereoisomeric structure of the binuclear cation. In the case of trien there are 8 possible chemically different isomers. On oxygenation of Co(trien)2+ in dilute solution 3 of those isomers seem to be formed preferentially. Their rate constants are separated over a factor of 50. For [(en)2 Co(O2, OH)Co(en)2]3+ there exist a meso form and a chiral structure. On oxygenation of Co(en)22+ in dilute solution the meso form and the racemate are formed to about equal amounts. The racemate dissociates about 5 times slower. Of the 3 possible achiral isomers of [(tren)Co(O2, OH)Co(tren)]3+ one is formed stereoselectively by oxygenation in solution.  相似文献   

2.
The [Co(tmen)3]3+ complex ion (tmen = 2,3-dimethylbutane-2,3-diamine) has been synthesized and its redox characteristics compared to those of its parent ion [Co(en)3]3+. The 12 peripheral Me groups significantly affect the properties of the [Co(tmen)3]3+ ion. The ligand-field bands are shifted to lower energies by about 1700 cm?1 compared to [Co(en)3]3+. The reduction potential for [Co(tmen)3]3+ is +0.28 V (vs. NHE) compared to ?0.18 V for [Co(en)3]3+. The rate of the self-exchange reaction for the [Co(tmen)3]3+/2+ couple, k = 8.5 × 10?8 M?1·S?1 was determined by applying the Marcus cross-relation with the reductants Cr2+, V2+, Eu2+, Ru2+, and [Co(sepulchrate)]2+.  相似文献   

3.
Several salts containing the cation Co(penten)3+, in which the hexamin «penten» (formula: page 625) acts as a sexadentate ligand, have been synthesized and characterized. Its optical antipodes have been separated in some of the salts (Fig. 4), and the rate of racemization studied. In strongly alkaline solution one of the 5 chelate rings slowly opens and Co(penten)OH2+ is produced (Fig. 1), to which a first proton can be attached at the terminal NH2-group (→ Co(Hpenten)OH3+), and a second which converts the hydroxo-complex into the aquo-complex (→ Co(Hpenten)OH4+). The equilibria between Co(penten)3+, Co(penten)OH2+, Co(Hpenten)OH3+ and Co-(Hpenten)OH24+ have been elucidated, and the kinetics of the ring opening and ring closing reactions have been studied. Ring opening and ring closure take place with retention of configuration. It proved impossible to open two of the chelate rings of Co(penten)3+. Cristalline salts with cations of the general formula Co(penten)X3?λ or Co (Hpeten)X4?λ, with Xλ? ? OH?, H2O, F?, Cl?, Br?, J?, SCN?, NO2,? and CO32?, have been obtained and characterized (Fig. 1, 2, 7 and Table 1).  相似文献   

4.
The octahedral cationic CoIII complexes [Co(ida)(bigH)2]+, [Co(glyO)(bigH)2]2+, [Co(α-alanO)(bigH)2]2+, [Co(β-alanO)BigH)2]2+ and Co(PhbigH)3]3+, where idaH2=iminodiacetic acid, glyOH=glycine, α-alanOH=α-alanine, β-alanOH=β-alanine and PhbigH=phenylbiguanide, were studied by thin-layer chromatography on silica gel in solutions of different electrolytes (NaCl, NaBr, NaI, Na2SO4, Na2S2O3, NaNO2 and NaNO3). Among other factors, the movement of the cationic complexes was found to be dependent on the surface tension and equivalent conductance of the developer electrolyte.  相似文献   

5.
Salting effects of metal chelate electrolytes Fe(phen)3Br2, Fe(bpy)3Br2, Co(phen)3Br2, Co(phen)3Br3, Co(en)3Br3, and Co(pn)3Br3 (where phen=1,10-phenanthroline, bpy=2,2-bipyridyl, en=ethylenediamine, and pn=1,2-propylenediamine) on the solubilities of nitrobenzene,o-,m-,and p-dinitrobenzenes (DNB), and toluene were studied in water at 25°C and compared to the results for sodium bromide and tetrabutylammonium bromide (Bu4NBr). The Co(phen) 3 3+ , Fe(phen) 3 2+ , and Fe(bpy) 3 2+ ions showed much stronger salting-in effects than did the Bu4N+ ion, while the effects of the Co(en) 3 3+ and Co(pn) 3 3+ ions are comparable with those of Bu4N+. A great dependence of salting-in on the polarity of dinitrobenzene isomers was found for Co(phen) 3 3+ and Fe(phen) 3 2+ . The results were related to the partial molal volume of the respective cations. The very strong salting-in was considered to be mainly due to hydrophobic hydrations of the metal chelate cations and partly due to van der Waals interactions between the aromatic ligands and the nonelectrolytes. The small salting-in effects by Co(en) 3 3+ and Co(en) 3 3+ were interpreted in terms of hydrogen bonding between oxygen atoms of the nitro compounds or the solvent water molecules and hydrogen atoms attached to nitrogens in the complexes.  相似文献   

6.
From the solubility of precipitated Co(OH)2 (s) determined radiometrically as a function of pH and ammonia content of the heterogeneous systems, the formation constants have been obtained for the following mononuclear hydroxo-, ammine- and mixed hydroxo-ammine-complexes: Co(OH)2, Co(OH)3?, Co(NH3)22+, Co(NH3)32+, Co(NH3)42+ and Co(OH)2 (NH3)2. The solubility of cobalt(II) hydroxide has also been calculated. The medium was 1M NaClO4 and the temperature 25° C.  相似文献   

7.
近十几年来,对小分子过渡金属配合物与大分子DNA键合与识别机理的研究一直是国际上生物无机化学领域十分活跃的研究课题[1 ̄3],已发展了一系列具有特定功能的配合物,如DNA结构探针和DNA荧光探针等。与其他类型的金属配合物相比,八面体过渡金属多吡啶配合物具有丰富的光化学和光物理信息,当这些配合物与DNA相互作用时,由于结构匹配或微环境的差异,配合物的光谱特征会出现不同程度的改变,从而达到对DNA的检测。传统的DNA荧光探针有[Ru(bpy)2dppz]2 和[Ru(phen)2dppz]2 (bpy=2,2′-联吡啶,phen=1,10-菲咯啉,dppz=二吡啶[3,2-a∶2′,3′…  相似文献   

8.
Abstract

The absolute configuration of an optically active Λ-[Co(EDDS)]? (EDDS = ethylene-diaminedisuccinate) complex was determined as Λ by the regional rule and spectroscopic data. The stereoselective ionic association between Λ-[Co(EDDS)]? and rac-[Co(en)3]3+ occurs preferentially between Λ-[Co(EDDS)]? and δ-[Co(en)3]3+. The stereoselective electron transfer reaction between Λ-[Co(EDDS)]? and rac-[Co(en)3]2+ has been investigated in aqueous solution, DMF and DMSO. Their enantiomeric excesses (e.e.) observed are 14%, 26% and 40% of δ-[Co(en)3]3+, respectively. The electron transfer reaction between Λ-[Co(EDDS)]? and conformationally restricted [Co(chxn)3]2+ has been examined in aqueous and DMSO solution. In aqueous solution, there are four isomers in the product which were determined as lel3, lel2ob, lelob2 , and ob3 of δ-[Co(chxn)3]3+ with optical purities of 22%, 25%, 11% and 10% e.e. respectively. In DMSO, the reaction produces lel3 -δ-and lel2ob-δ-[Co(chxn)3]3+ with optical purities of 100% and 75% e.e. respectively.  相似文献   

9.
Two series of cobalt(III) complexes were synthesized and spectrally analyzed, [Co(2,2′-bipyridyl)2(aa)]I2 and [Co(1,10-phenanthroline)2(aa)]I2 (where the letters aa refer to an optically active, bidentate amino acid). The following amino acids were used: l-alanine, glycine, l-leucine, l-phenylalanine, and l-proline.This research is an analogue to the chemical systems studied by Mason et al.1,2 They investigated complexes such as [Co(phen)3]3+, [Co(dipy)3]3+, [Co(phen)2(dipy)]3+, [Co(dipy)2(phen)]3+, [Co(phen)2(ox)]2+, and [Co(dipy)2(ox)]2+. The series of [Co(dipy)2(na)]2+ and [Co(phen)2(na)]2+ complexes, where the letters na refer to a non-optically active, bidentate ligand, have exhibited exciton-splitting. We used optically active amino acids to ascertain whether or not the exciton-splitting phenomenon would occur when a non-optically active ligand was substituted by an optically active amino acid. In addition, a series of optically active amino acids was selected with the intention of determining whether small differences among the amino acid ligands would affect the circular dichroism (CD) spectra of the different complexes and if the formation of these complex ions would be steroselective.  相似文献   

10.
Substitution-inert metal complexes, [Co(edda)(H2O)2]+, (Co(edda)(en)]+, [Co(edda)(dmen)]+, [Co(en)2-(gly)]2+, [Co(en)2(acac)]2+, and [Co(trien)(gly)]2+ in their nitrate salt solutions are used as eluents in nonsuppressed cation chromatography (where edda = ethylenediamine-N,N′-diacetic acid, en = ethylenediamine, dmen = N,N′-dime-thylethylenediamine, gly = glycine, acac = acetylacetone, and trien = triethylenetetraamine). It is found that all the mono- and di-valent charged complexes can be used to separate alkali and alkaline earth metal cations, respectively. The separations for monovalent cations are sometimes comparable to those using ultrapure HNO3 solutions. However, the divalent Ca2+ and Sr2+ ions cannot be resolved using the metal complex eluents. On the other hand, a selected, direct non-suppressed IC separation of zinc(II) and cadmium(II) ions is demonstrated for the first time using a substitution-inert metal complex eluent and a conductivity detector. Comparisons of these eluents with those reported previously, i. e. HNO3 and ethylenediammonium salt solution are made and explanations are proposed to account for the different selectivities observed where possible. The future development of this technique is also briefly discussed.  相似文献   

11.
The electrochemical properties of n-sulfonatothiacalyx[4]arene (H4XNa4) complexes with [Co(dipy)3]3+ and Fe3+ ions were studied by means of cyclic voltammetry in aqueous solution at pH 2.5. The observed single-electron reduction of [Co(dipy)3]3+ bound extraspherically to the upper rim and Fe3+ ion bound intraspherically to the lower rim of n-sulfonatothiacalyx[4]arene in binary [Co(dipy)3]3+ · H3X5?, H3X5? · Fe3+, and ternary [Co(dipy)3]3+ · H3X5? · Fe3+ heterometal complexes was more difficult than in the free state. The reversible single-electron transfer to the metal ion results in lower binding energy ([Co(dipy)3]3+, ΔΔG 0 = 3.9 kJ/mol) or in full fast dissociation of the complex (Fe3+). The ternary complex in the solution forms the aggregates, in which inner encapsulated Fe(III) and Co(III) ions are not reduced on the electrode. Their quantitative reduction takes place by the relay mechanism of intra- and intermolecular electron transfer through electrochemically generated [Co(dipy)3]2+ outer ions.  相似文献   

12.
The volumes of activation in cm3 mol?1 for the aquation of Co(CN)5X3? were determined at 40°C and μ = 1 M (NaClO4) to be + 7.8 ± 0.5 for X = Cl?, + 7.6 ± 0.6 for X = Br?, + 14.0 ± 0.7 for X = I?, and + 16.8 ± 0.5 for X = N3? (0.1 M HClO4), respectively. The volumes of activation for the aquation of Co(CN)5Cl3? at μ = 0.1 M are + 10.0 ± 0.6 cm3 mol?1 and ± 9.1 ± 0.3 cm3 mol?1 at 40°C and 25°C, respectively. The corresponding values for the anation of Co(CN)5OH22? (at 40°C) and μ = 1 M by Br?, I?, and NCS? are +8.4 ± 1.0, +9.4 ± 1.6, and +8.2 ± 0.9 cm3 mol?1, respectively. These data are discussed in terms of a dissociative (D) mechanism.  相似文献   

13.
Reactions of oxygenated cobalt(II) complexes. IX. Oxidative properties of tetrakis(ethylenediamine)-μ-peroxo-μ-hydroxo-dicobalt(III)
  • 1 VIII s. [1].
  • [(en)2Co(O2, OH)Co(en)2]3+ ( a ) reacts with I? in acidic aqueous solution according to: CoIII(O2, OH)CoIII + 21? + 5H+ ? 2CoIII + 3H2O + I2. Using I? in excess first order rate constants are obtained which, to a first approximation, are independent of [I?]. Comparison with kinetic data of deoxygenation of [(en)2Co(O2, OH)Co(en)2]3+ under analogous conditions suggests that both reactions have the same rate determining step. The singly bridged species [(en)2(H2O)CoO2Co(H2O) (en)2]4+ is shown to be the reactive intermediate in the iodide oxidation (Schema 2).  相似文献   

    14.
    Single phase perovskite-based rare earth cobaltates (Ln1−xSrxCoO3−δ) (Ln=La3+, Pr3+, Nd3+, Sm3+, Gd3+, Dy3+, Y3+, Ho3+, Er3+, Tm3+ and Yb3+; 0.67?x?0.9) have been synthesized at 1100°C under 1 atmosphere of oxygen. X-ray diffraction of phases containing the larger rare earth ions La3+, Pr3+ and Nd3+ reveals simple cubic structures; however electron diffraction shows orientational twinning of a local, tetragonal (I4/mmm; ap×ap×2ap) superstructure phase. Orientational twinning is also present for Ln1−xSrxCoO3−δ compounds containing rare earth ions smaller than Nd3+. These compounds show a modulated intermediate parent with a tetragonal superstructure (I4/mmm; 2ap×2ap×4ap). Thermogravimetric measurements have determined the overall oxygen content, and these phases show mixed valence (3+/4+) cobalt oxidation states with up to 50% Co(IV). X-ray diffraction data and Rietveld techniques have been used to refine the structures of each of these tetragonal superstructure phases (Ln=Sm3+-Yb3+). Coupled Ln/Sr and oxygen/vacancy ordering and associated structural relaxation are shown to be responsible for the observed superstructure.  相似文献   

    15.
    Zusammenfassung Folgende Koordinationsformen entstehen aus [Co(HMPT)4]2+ bei Zusatz von Halogenidionen in Hexamethylphosphorsäuretriamid (HMPT): [Co(HMPT)3Cl]+, [Co(HMPT)2Cl2], [Co(HMPT)Cl3], [CoCl4]2–, [Co(HMPT)3Br]+, [Co(HMPT)2Br2] und [Co(HMPT)3J]+.
    Hexamethylphosphoric triamide as a ligand II: Reactions of Co(HMPT)4 2+ with chloride, bromide, and iodide ions
    The following coordination species are formed from [Co(HMPT)4]2+, by addition of halide ions in hexamethylphosphoric triamide (HMPT): [Co(HMPT)3Cl]+, [Co(HMPT)2Cl2], [Co(HMPT)Cl3], [CoCl4]2–, [Co(HMPT)3Br]+, [Co(HMPT)2Br2] and [Co(HMPT)3J]+.


    Mit 7 Abbildungen

    V. Gutmann, A. Weisz undW. Kerber, 1. Mitt., Mh. Chem.100, 2096 (1969).  相似文献   

    16.
    Activity coefficients of [Co(en)3](NO3)3 and [Co(en)3](ClO4)3, to be compared with [Co(en)3]Cl3 and the corresponding lanthanum salts previously studied, are determined. [Co(en)3]Cl3 data are revised. Ion interaction strengths vary in the same order found for La3+, i.e., as if nitrate and perchlorate ions were of smaller and larger size, respectively, than chloride ions; however, the differences are much smaller than in lanthanum salts. Tris(ethylenediamine)cobalt III and lanthanum nitrate, chloride, and perchlorate—like the corresponding hexacyanoferrate(III) and hexacyanocobaltate(III) salts, but contrary to sulfate salts—behave as if [Co(en)3]3+ were smaller in size than La3+. In the dilute regions, [Co(en)3](NO3)3 displays negative deviations from the limiting slope, a kind of behavior typical for 2:2, 2:3, 3:2, and 3:3 electrolytes, but unnoticed earlier for 3:1 or 1:3 electrolytes. Pitzer's equation parameters able to provide accurate activity and osmotic coefficients for [Co(en)3](NO3)3, [Co(en)3](ClO4)3, and, revised, [Co(en)3]Cl3 are reported.  相似文献   

    17.
    The structures and stability of outer-sphere associates of sulfonate derivatives of thiacalix[4]arene and calix[4]resorcinarene with coordinatively saturated cobalt(iii) bis- and tris-chelates ([Co(L-His)2]+, [Co(en)2ox]+, [Co(en)3]3+, and [Co(dipy)3]3+) were compared based on the data from UV, CD, 1D 1H NMR, and 2D (2D NOESY) 1H NMR spectroscopy and conductometry. Outer-sphere association is accompanied by partial penetration of the chelate rings of the complexes into the hydrophobic cavity of calixarene, which induces changes in the spectroscopic and spectropolarimetric properties of the cobalt(iii) complexes.  相似文献   

    18.
    Photolysis of Mixed-Ligand Cobalt(II1) Complexes with α-Aminoacids, Ethylenediamine, and 2,2′-Bipyridyl. Elimination of Ligand Fragments A new organo-cobalt(III) complex, [Co(bipy)22-CH2NH2)]2+, have been obtained from UV-irradiated aqueous solutions of [Co(gly)2bipy]+, [Co(bipy)2gly]2+, [Co(bipy)(en)gly]2+, and [Co(en)2bipy]3+ by ion-exchange chromatography and characterized both analytically and by IR, NMR, and UV/VIS spectra. The formation of the same product in all cases with the η2-aminomethyl ligand is explained by photoinduced elimination of the ligand fragments (CO2 from the glycinato or CH2NH2+ from the ethylenediamine ligand) and subsequent ligand exchange reactions which are catalyzed by CoII species. Similar photolysis products of sarcosinato or valinato complexes were found to be less stable, and hence they could be observed only at low temperatures.  相似文献   

    19.
    《Analytical letters》2012,45(3):493-507
    Abstract

    The electrochemical reduction of 2,2′-bipyridine (bipy) complexes of cobalt (II), [Co(bipy)3]2+, in aqueous medium has been studied with dc tast, normal pulse polarography and controlled-potential coulometry. The cathodic wave in the process [Co(bipy)3]2+/[Co(bipy)3]+ shows catalytic character in the presence of hydrogen ions. The rate constant of the parallel chemical reaction was found to be 2.2 × 104 M?1. s?1.  相似文献   

    20.
    Zusammenfassung Auf Grund spektrophotometrischer, potentiometrischer und konduktometrischer Befunde entstehen aus [Co(HMPT)4]2+ in Hexamethylphosphorsäuretriamid (HMPT) bei Zusatz von Pseudohalogenidionen folgende Koordinationsformen: [Co(HMPT)3N3]+, [Co(HMPT)2(N3)2], [Co(HMPT)(N3)3], [Co(N3)4]2–, [Co(HMPT)3NCS]+, [Co(HMPT)2(NCS)2], [Co(HMPT)(NCS)3], [Co(NCS)4]2–, [Co(HMPT)2(CN)2], [Co(HMPT)(CN)3], [Co(HMPT)(CN)5]3–.
    Hexamethyl phosphoric triamide as a ligand, III: Reactions of [Co(HMPT)4]2+ with rhodanide, cyanide, and azide ions, resp
    Spectrophotometric, potentiometric and conductometric results indicate that addition of pseudohalide ions to [Co(HMPT)4]2+ in hexamethylphosphoramide (HMPT) leads to the following coordination forms: [Co(HMPT)3N3]+, [Co(HMPT)2(N3)2], [Co(HMPT)(N3)3], [Co(N3)4]2–, [Co(HMPT)3NCS]+, [Co(HMPT)2(NCS)2], [Co(HMPT)(NCS)3], [Co(NCS)4]2–, [Co(HMPT)2(CN)2], [Co(HMPT)(CN)3], [Co(HMPT)(CN)5]3–.


    Mit 7 Abbildungen

    2. Mitt.:V. Gutmann undA. Weisz, Mh. Chem.100, 2104 (1969).  相似文献   

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