首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 328 毫秒
1.
Summary The oxidation of MnII by S2O8 2– to MnVII in phosphoric acid medium proceeds via a stable MnIII and MnIV species. The reaction is catalysed by Ag+ and exhibits first order dependence on [S2O8 2–], [Ag+] and, is independent of [MnII]. The [H+] has no significant effect on the reaction. It is observed that the PO4 3– ion stabilises the transient manganese(III) and manganese(IV) species by forming a stable and soluble phosphato-complexes. The activation parameters for the two stages of oxidation, namely MnII MnIV and MnIVMnVII at 25° C are Ea=52 ±4 kJ mole–1, S*=–57±2 JK–1 mole–1 and Ea =56±4 kJ mole–1, S*=–44±2 JK–1 mole–1, respectively. A mechanism consistent with the experimental observations is proposed.Presented at the National Symposium on Reaction Kinetics and Mechanism, Department of Chemistry, University of Jodhpur, Jodhpur, India, Nov. 15–18, 1986.  相似文献   

2.
The kinetics of the formation and decomposition of MnIII have been investigated spectrophotometrically in acidic media at 25 °C. The complete rate law for MnIII formation isCrVI + DMF + MnII {H+} MnIII + CO2 + Me2NH + CrIII ... (1)MnIII + DMF {H+} MnII + CO2 + Me2NH ... (2)expressed by k obs1 = k 1 k1 K a1[H+][DMFH+][MnII]/{1 + K a1[H+]}. MnIII reduction by DMF follows the rate law k obs2 = k 2 K h[DMF][H+]2/{[H+] + K h}. The above results are accounted for by a mechanism involving the intermediacy of CrIV.  相似文献   

3.
Summary Four novel MnII binuclear complexes have been prepared and characterized, namely: [Mn2(TBPHTA)(L)4](ClO4)2 [L = 2,2-bipyridyl (bipy), 1,10-phenanthroline (phen), 4,4-dimethyl-2,2-bipyridyl (Me2bipy) and 5-nitro-1,10-phenanthroline (NO2-phen), respectively], and TBPHTA = the tetrabromophthalate dianion. Based on i.r. spectra, elemental analyses and conductivity measurements, extended tetrabromophthalato-bridged structures consisting of two MnII ions, in which each MnII ion has a distorted octahedral environment, are proposed for these complexes. The temperature dependence of the magnetic susceptibility for [Mn2(TBPHTA)(phen)4] (ClO4)2·H2O was measured over the 4–300 K range and the observed data were successfully simulated by an equation based on the spin Hamiltonian operator ( = -2J 1 2), giving the exchange integral J = -1.22 cm–1. This result indicates a weak antiferromagnetic spin exchange interaction between the metal ions.  相似文献   

4.
Summary MnII forms a yellow mononuclear species with the title ligand having a 12 stoichiometry and whose conditional stability constant is 8.9 × 1010 m –2. The c.v. of this complex shows an oxidation at +0.78V versus s.c.e. Controlled-potential electrolysis at +0.80V versus s.c.e. yields a binuclear species of MnIII with a 12 metal:ligand stoichiometry.The addition of MnIII(urea)6(ClO4)3 to a solution of the ligand produces a mononuclear complex of MnIII if the concentration of the metal ion is less than 1 mM. At higher concentrations a binuclear species is obtained. The latter is reduced in two steps, at +0.24 and –0.58 V versus s.c.e. Controlled-potential electrolysis at 0.0 V produces a dark green complex after the transfer of 0.5 equivalents of charge per mole of Mn. This binuclear L2MnII-MnIIIL2 mixed-valence complex can be obtained only by electrolysis of the binuclear L2MnIIIMnIIIL2 species. Attempts to prepare the complex chemically were unsuccessful - the binuclear MnIII species was obtained in every case.Author to whom all correspondence should be directed.  相似文献   

5.
Summary The synthesis of the NiII, PdII and CuII complexes of N, N-bis(aminoalkyl)oxamides (LH2) is described and structures are proposed on the basis of their physical and spectroscopic properties. With NiII and PdII only one complex is formed with general formula NiL or PdL, characterised by coordination through two deprotonated amide N-atoms and two terminal NH2 groups. With CuII it proved possible to obtain three structurally different compounds, depending on the pH, with general formulae Cu(LH2)X2, Cu2(L)X2 and CuL in which X=Cl, Br or NO3. The structure of [Cu2(C8O2N4H16](NO3)2 was solved by means ofx-ray diffraction; Mr=451.33, monoclinic, space group P21/n, a=9.503(4), b=7.614(1), c=10.407(3) Å, =98.43(3)°, V=744.3(7)Å3, Z=2, Dx=1.202 g cm–3, =1.33 cm–1, (MoK)=0.71073 Å, F(000)=520, room temperature, R=0.043, wR=0.047 for 1080 observed [I>-3(I)] not systematically absent reflections out of 1423 measurements and 137 variables. The compound has a conformational chair/boat disorder with 82% in the more stable chair form.  相似文献   

6.
Summary Dichloro complexes of PdII, [Pd(L–L)Cl2], where L–L=1-(thiomethyl)-2-(diphenylarsino)ethane (S–As) or 1-(thiomethyl)-2-(diphenylphosphino)ethane (S–P) andtrans-[PdL2Cl2], where L=diphenyl(2-phenylethyl)-phosphine (PE), diphenyl(1-naphthyl)phosphine (PN) orN-methyl-2-thiophenealdimine (SN), have been prepared and characterized. The reactions of these complexes with MeLi were investigated. The dimethyl complexes [Pd(L–L)Me2] (L–L=S–As, S–P) and [Pd(PE)Me2] were isolated and characterized. Reaction of [Pd(L–L)Me2] (L–L=S–As, S–P) with HCl affords the monomethyl derivatives [Pd(L–L)Me(Cl)]. In contrast to the Pt analogues, [Pd(L–L)Me2] and [Pd(L–L)Me(Cl)] are relatively less stable than [Pt(L–L)Me2] and [Pt(L–L)Me(Cl)].  相似文献   

7.
Summary Two novel MnII-MnIII-MnII oxalato complexes have been synthesized and characterized, namely [Mn2Mn(ox)3(L)4](ClO4) [L = 1,10-phenanthroline (phen) or 5-nitro-1,10-phenanthroline (NO2-phen), respectively], where ox stands for the oxalate dianion. Based on i.r., elemental analyses and electronic spectra, these complexes are proposed to have extended oxalatobridged structures consisting of MnII and MnIII ions, in which MnIII and each MnII ion has a distorted octahedral environment. The temperature dependence of magnetic susceptibility for [Mn2Mn(ox)3(phen)4] (ClO4) was measured over the 4.1–300 K range and the observed data were successfully simulated by an equation based on the spin-Hamiltonian operator ( = -2J( 1 2 + 2 3)), giving the exchange integral J = -1.57cm–1. This indicates weak antiferromagnetic spin exchange interaction between MnII and MnIII ions.  相似文献   

8.
The energy of activation of CH 3 . radical rupture from the radical (CH3)2juvyCCH(CH3)2 is 142.2 kJ mol–1; the selfcombination rate constant is kc {(CH3)2juvyCCH(CH3)2}=107.3 dm3 mol–1 s–1.
CH 3 . (CH3)2juvyCCH(CH3)2 142,2 /, kc {(CH3)2juvyCCH(CH3)2}=107,3 3–1 –1.
  相似文献   

9.
We describe the synthesis, characterization and electrochemistry of a new family of peripherally functionalised vic-dioxime, 5,6-bis-(hydroxyimino)-1,2,9,10-hydroxy-4,7-dithiadecane (LH2), with bis-(thiopropandiol) moieties attached to the oxime. Thiopolyalcohol groups containing two different heteroatoms (—S— and —O—) serve as weak exocyclic binding sites for Pd+2 and Ag+ ions. Novel mononuclear (LH)2M, (M = NiII, CuII, CoII, MnII and FeII), homodinuclear (LH)2(UO2)2(OH) and heterotrinuclear (LH)2MM2 (M = NiII and M = PdII and AgI) species have been obtained with the metal:ligand ratios of 1:2, 2:2, and 3:2 respectively. Metal ions coordinate through N,N of the oxime and S,O donor sites of the peripherally attached groups in the presence of the base. The heterotrinuclear complexes were prepared by the interaction of the mononuclear complex, (LH)2Ni, with Pd(C5H5)2 and AgNO3 in an appropriate solvent. The complexes were characterized by elemental analysis, 1H-n.m.r., u.v.–vis. spectroscopy, FT-IR., and by f.a.b-m.s. The redox properties of the complexes were studied by cyclic voltammetry.  相似文献   

10.
Summary A series of mixed-ligand complexes of group VIII metals, M(DIAFO)2(NCS)2 and M(DIAFH)2X2 (M = FeII, CoII, NiII, X = NCS, Cl) with the 3,3-bridged derivative of 2,2-bipyridyl (bipy) (1) were prepared, where DIAFO (2) and DIAFH (3) are 4,5-diazafluoren-9-one and 4,5-diazafluoren-9-hydrazone, respectively. These complexes were investigated by i.r., u.v.-vis-near i.r. spectroscopy and by variable-temperature magnetic susceptibility measurements. The electronic spectra show that the two ligands exert a field strength far removed from the FeII cross-over value. All the complexes are paramagnetic, following the Curie-Weiss law in the 77–300 K range. A typical crystal structure of Co(DIAFO)2(NCS)2 for these compounds was determined with orthorhombic, space group Pcan, a = 10.377(5) Å, b = 13.289(6) Å, c= 16.629(7) Å, V = 2293(2) Å3, D c = 1.563 g cm–3, F(000) = 1091.74, Z = 4, R = 0.043, R = 0.047. Steric effects are thought to be operative in both ligands studied, but are weaker than those of the typical bidentate diimine ligand bipy.Author to whom all correspondence should be directed.  相似文献   

11.
The macrocycle, L, prepared by template condensation of bis-6,6-(-methylhydrazino)-4-phenyl-2,2:6,2-terpyridine with glyoxal, forms a stable crystalline MnII complex, [Mn(L)(H2O)2][PF6]2, which has been used as a starting material for electrochemical studies on a series of seven coordinate MnII complexes [Mn(L)X2]2+ (X = pyridine, 4-cyanopyridine, 4-aminopyridine, 4-dimethylaminopyridine, pyrazine, imidazole 1-methylimidazole, 2-dimethylimidazole or Ph3P). Cyclic voltammetry of the complexes in MeCN shows a reversible one electron reduction wave in the range –1.32 to –1.42 V versus the Ag/AgBF4 reference electrode.  相似文献   

12.
A new vic-dioxime, 13,14-bis-(hydroxyimino)-9,12,15,18-diazadithiaoctacosane, has been synthesized from 2-octylsulfanylaminobenzene and (E,E)-dichloroglyoxime. Mononuclear transition metal complexes of NiII, CuII, CoII and FeII have been prepared and were found to have a metal–ligand ratio of 1:2. The synthesis of di- and trinuclear complexes was achieved with UIVO2 and CuII depending on the stoichiometry of the reactants. The complexes were characterized by elemental analysis, 1H-n.m.r., u.v.–vis, i.r., f.a.b.-m.s. and by cyclic voltammetry.  相似文献   

13.
A new potential tetradentate ligand, N-nicotinoyl-N-2-furanthiocarbohydrazide (H2Nfth), and its complexes with VOIV, MnII, FeII,III, CoII, NiII, CuII and ZnII have been prepared and characterized by elemental analyses, magnetic susceptibility measurements, u.v.–vis, i.r., n.m.r., ES+ and FAB mass spectral data. The room temperature e.s.r spectra of the VOIV and FeIII complexes yield g values, characteristic of octahedral complexes. The Mössbauer spectra of [Fe(HNfth)2] and [Fe2(Nfth)3] at room temperature and at 78 K suggest the presence of high-spin iron(II) and iron(III), respectively. The complexes are electrically insulating at room temperature, however, their conductivities increase as the temperature increases from 333–383 K, with a band gap of 0.46–0.77 eV, indicating their semiconducting behaviour. H2Nfth and its soluble complexes have been screened against several bacteria and fungi.  相似文献   

14.
SO 3 radicals are formed during the reaction between SO2 and MnO2-alumina, which suggests that SO 3 take part in the reduction of Mn4+ to Mn2+.
SO2 MnO2/Al2O3 SO 3 , , SO 3 Mn4+ Mn2+.
  相似文献   

15.
Summary It has been found that in alkaline triethanolamine medium the complex of bivalent manganese is oxidised by hexacyanoferrate(III), hydrogen peroxide or lead dioxide to the red-coloured complex of MnIV, which can be titrated potentiometrically with ferrous salt solution (MnIV MnIII and MnIII MnII). The stability of this complex has been studied in dependence on the oxidant employed, and it has been found that lead dioxide is best suited for this oxidation process. Similarly the oxidation of the complex CoII CoIII has been studied in the same medium, and conditions have been found for the reductometric determination of the CoIII complex formed.The possibilities for determining manganese in the presence of cobalt and of other accompanying elements are discussed. The results obtained have been applied to the determination of manganese in ores and alloys.
Zusammenfassung Bei Untersuchungen zum Oxydations-Reduktions-Verhalten von Mangan und Kobalt in alkalischer Triäthanolaminlösung wurde gefunden, daß der MnII-Komplex durch Hexacyanoferrat(III), Wasserstoffperoxid oder Bleidioxid zum rotgefärbten MnIV-Komplex oxydiert wird, der potentiometrisch mit, FeII-Lösung titriert werden kann (MnIV MnIII; MnIII MnII). Die Stabilität des Komplexes wurde in Abhängigkeit von der Art des Oxydationsmittels geprüft und Bleidioxid als am günstigsten gefunden. Analog wurden auch die Oxydation des CoII- zum CoIII-Komplex untersucht und Bedingungen zur reduktometrischen Bestimmung des letzteren ausgearbeitet. Die Möglichkeiten zur Manganbestimmung in Gegenwart von Kobalt sowie anderen Begleitelementen werden diskutiert, und als praktische Anwendung wird die Manganbestimmung in Erzen und Legierungen beschrieben.


Dedicated to Prof. Dr. M. von Stackelberg on his 70th birthday.  相似文献   

16.
Summary Complexes of manganese(II) and iron(II) picrates with various bidentate (L) and monodentate (L) heterocyclic bases have been synthesised; their compositions have been established as [ML3]A2 (1), [ML2 · 2 H2O]A2 (2), [ML6]A2 (3) and [ML4 · 2 H2O]A2 (4), where M = FeII and MnII, L = 2,2-bipyridyl (bipy) and 1,10-phenanthroline (phen) in (1), A = picrate anion; M = MnII, L = bipy and phen in (2); M = FeII, L = pyridine (py), 4-picoline (4-pic) and 3-picoline (3-pic) in (3); M = MnII, L = py, 4-pic, quinoline (quin) and 2,6-lutidine (2,6-lut) in (4) and also M = FeII, L = quin and 2,6-lut.  相似文献   

17.
Summary The metal complexes of the type [M(SB)2(H2O)2] and [M(SB)2][where M = MnII, CoII, NiII or CuII, M = ZnII CdII, HgII and PbII and SBH = 2-(2-hydroxyacetophenone)imino-5-(p-anisyl)-1,3,4-oxadiazole] have been prepared and characterised by elemental analyses, thermal analyses, magnetic measurements, electronic and infrared spectral studies. The complexes [M(SB)2(H2O)2] possess octahedral structures, whereas complexes [M(SB)2] are tetrahedral. The crystal field parameters of the CoII and NiII complexes are also calculated.  相似文献   

18.
A comparison of the properties of iron-containing catalysts prepared through carbonyl clusters Fe3(CO)12 and (NEt4)2[Fe2Mn(CO)12] and iron and manganese nitrates in CO hydration indicates that the addition of Mn incorporated in (NEt4)2[Fe2Mn(CO)12] decreases the methane yield and increases the portion of higher hydrocarbons.
, Fe(CO)12 (NEt4)2[Fe2Mn(CO)12] , CO. Mn (NEt4)2[Fe2Mn(CO)12] .
  相似文献   

19.
Summary The reversible complex formation between 2-(2-aminoethyl) benzimidazole (AEB) and nickel(II) was studied by stopped flow spectrophotometry at I = 0.30 mol dm–3. Both the neutral and monoprotonated form of AEB reacted to give the NiAEB2+ chelate. At 25 °C, the rates and activation parameters for the reactions NiII + AEB NiAEB2+ and NiII + AEBH+ NiAEB2+ + H+ are k f L(dm–3 mol–1 s–1) = (2.17 ± 0.24) × 103, H (kJ mol–1) = 40.0 ± 0.8, S (JK–1 mol–1) = – 47 ± 3 and k inff pHL (dm3 mol–1 s–1) = 33 ± 10, H (kJ mol–1) = 42.0 ±2.7, S (JK–1 mol–1) = – 72 ± 9. The dissociation of NiAEB2+ was acid catalysed and k obs for this process increased linearly with [H+] in the 0.01–0.15 mol dm–3 (10–30 °C) range with k H(dm3 mol–1s–1) (25 °C) = 329 ± 6, H (kJ mol–1) = 40 ± 2 and S (JK–1 mol–1) = – 61 ± 8. The results also indicated that the formation of NiAEB2+ involves a chelation-controlled, rate-limiting process. Analysis of the S ° data for the acid ionisation of AEBH inf2 p2+ and the formation of NiAEB2+ showed that the bulky AEBH+ ion has a solvent structure breaking effect as compared to AEB [s aqS ° (AEBH+) – s aq ° (AEB) = 69 JK–1 mol–1], while AEBH inf2 p2+ is a solvent ordering ion relative to NiAEB2+ [s aq° (NiAEB2+) – ovS aq ° (AEBH inf2 p2+ ) = 11 JK–1 mol–1].Author to whom all correspondence should be directed.  相似文献   

20.
Pyridine-2-carboxaldehyde reacts with /-naphthylamine to give /-naphthyl-(2-pyridylmethylene)amine [-L (1), -L (2)]. L belongs to the unsymmetric diimine (—N=C—C=N—) family which can form five–membered chelate rings with metal ions. {donor centers are abbreviated as N[N(Py)] and N [N(nap)]} [Ag(L)2]+ complexes were prepared and characterized by spectroscopic data. The reaction between L and RuCl3 in boiling EtOH yielded green and blue–green compounds of composition RuCl2(L)2. I.r., u.v.–vis. and 1H-n.m.r. data determined the stereochemistry of the complexes as trans-cis-cis (green) and cis-trans-cis (blue–green) according to the sequence of the coordination pair of Cl, N [N(Py)] and N [N(nap)]. Upon treatment of Ag(L)2 + with Ru(bpy)2Cl2 in alcoholic suspension the ternary complexes, [Ru(bpy)2(L)](ClO4)2, were isolated and characterized by spectroscopic data. [Ru(bpy)(L)2](ClO4)2 complexes were synthesized similarly from ctc-Ru(L)2Cl2 and 2,2-bipyridine (bpy) in the presence of AgNO3 and NaClO4. These complexes show well-defined m.l.c.t transitions in the visible region. The sterochemistry of the complexes was established by 1H-n.m.r. data. Cyclic voltammetry shows a high potential RuIII/RuII couple and follows the order: [Ru(bpy)(L)2]2+ > [Ru(bpy)2(L)]2+ > Ru(-L)2Cl2 > Ru(-L)2Cl2.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号