TY - JOUR A1 - Ast, Sandra A1 - Fischer, Tobias A1 - Müller, Holger A1 - Mickler, Wulfhard A1 - Schwichtenberg, Mathias A1 - Rurack, Knut A1 - Holdt, Hans-Jürgen T1 - Integration of the 1,2,3-Triazole "Click" Motif as a potent signalling element in metal ion responsive fluorescent probes JF - Chemistry - a European journal N2 - In a systematic approach we synthesized a new series of fluorescent probes incorporating donoracceptor (D-A) substituted 1,2,3-triazoles as conjugative -linkers between the alkali metal ion receptor N-phenylaza-[18]crown-6 and different fluorophoric groups with different electron-acceptor properties (4-naphthalimide, meso-phenyl-BODIPY and 9-anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge-transfer (CT) type probes 1, 2 and 7, the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge-separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting-up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7, which contains a 9-anthracenyl moiety as the electron-accepting fluorophore, is the only probe which retains light-up features in water and works as a highly K+/Na+-selective probe under simulated physiological conditions. Virtually decoupled BODIPY-based 6 and photoinduced electron transfer (PET) type probes 35, where the 10-substituted anthracen-9-yl fluorophores are connected to the 1,2,3-triazole through a methylene spacer, show strong ion-induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3-triazole fluoroionophores. KW - charge transfer KW - click chemistry KW - electron transfer KW - fluorescent probes KW - metal ions Y1 - 2013 U6 - https://doi.org/10.1002/chem.201201575 SN - 0947-6539 VL - 19 IS - 9 SP - 2990 EP - 3005 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Awad, Duha Jawad A1 - Koch, Andreas A1 - Mickler, Wulfhard A1 - Schilde, Uwe A1 - Strauch, Peter T1 - EPR spectroscopy of 4, 4 '-Bis(tert-butyl)-2, 2 '-bipyridine-1, 2-dithiolatocuprates(II) in host lattices with different coordination geometries JF - Zeitschrift für anorganische und allgemeine Chemie N2 - A series of new heteroleptic MN2S2 transition metal complexes with M = Cu2+ for EPR measurements and as diamagnetic hosts Ni2+, Zn2+, and Pd2+ were synthesized and characterized. The ligands are N2 = 4, 4'-bis(tert-butyl)-2, 2'-bipyridine (tBu2bpy) and S2 =1, 2-dithiooxalate, (dto), 1, 2-dithiosquarate, (dtsq), maleonitrile-1, 2-dithiolate, or 1, 2-dicyanoethene-1, 2-dithiolate, (mnt). The CuII complexes were studied by EPR in solution and as powders, diamagnetically diluted in the isostructural planar [NiII(tBu2bpy)(S2)] or[PdII(tBu2bpy)(S2)] as well as in tetrahedrally coordinated[ZnII(tBu2bpy)(S2)] host structures to put steric stress on the coordination geometry of the central CuN2S2 unit. The spin density contributions for different geometries calculated from experimental parameters are compared with the electronic situation in the frontier orbital, namely in the semi-occupied molecular orbital (SOMO) of the copper complex, derived from quantum chemical calculations on different levels (EHT and DFT). One of the hosts, [NiII(tBu2bpy)(mnt)], is characterized by X-ray structure analysis to prove the coordination geometry. The complex crystallizes in a square-planar coordination mode in the monoclinic space group P21/a with Z = 4 and the unit cell parameters a = 10.4508(10) angstrom, b = 18.266(2) angstrom, c = 12.6566(12) angstrom, beta = 112.095(7)degrees. Oxidation and reductions potentials of one of the host complexes, [Ni(tBu2bpy)(mnt)], were obtained by cyclovoltammetric measurements. KW - 1 KW - 2-Dithiosquarate KW - 1 KW - 2-Dithiooxalate KW - 1 KW - 2-Dicyanoethene-1 KW - 2-dithiolate KW - 4 KW - 4'-Bis(tert-butyl)-2 KW - 2'-bipyridine KW - X-ray structure KW - EPR KW - Copper KW - Nickel KW - Zinc Y1 - 2012 U6 - https://doi.org/10.1002/zaac.201100517 SN - 0044-2313 VL - 638 IS - 6 SP - 965 EP - 975 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Benassi, Rois A1 - Bregulla, Antje A1 - Friedrich, Alwin A1 - Henning, Dietrich A1 - Heydenreich, Matthias A1 - Mickler, Wulfhard A1 - Kleinpeter, Erich A1 - Kempter, Gerhard A1 - Schilde, Uwe A1 - Taddei, F. T1 - NMR spectroscopic and theoretical structural study of 5-exo-methylene-substituted hydantoins Y1 - 1998 ER - TY - JOUR A1 - Brietzke, Thomas Martin A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Mickler, Wulfhard A1 - Holdt, Hans-Jürgen T1 - Heterodinuclear Ruthenium(II) Complexes of the Bridging Ligand 1,6,7,12-Tetraazaperylene with Iron(II), Cobalt(II), Nickel(II), as well as Palladium(II) and Platinum(II) JF - Zeitschrift für anorganische und allgemeine Chemie N2 - The first heterodinuclear ruthenium(II) complexes of the 1,6,7,12-tetraazaperylene (tape) bridging ligand with iron(II), cobalt(II), and nickel(II) were synthesized and characterized. The metal coordination sphere in this complexes is filled by the tetradentate N,N-dimethyl-2,11-diaza[3.3](2,6)-pyridinophane (L-N4Me2) ligand, yielding complexes of the general formula [(L-N4Me2)Ru(mu-tape)M(L-N4Me2)](ClO4)(2)(PF6)(2) with M = Fe {[2](ClO4)(2)(PF6)(2)}, Co {[3](ClO4)(2)(PF6)(2)}, and Ni {[4](ClO4)(2)(PF6)(2)}. Furthermore, the heterodinuclear tape ruthenium(II) complexes with palladium(II)- and platinum(II)-dichloride [(bpy)(2)Ru(-tape)PdCl2](PF6)(2) {[5](PF6)(2)} and [(dmbpy)(2)Ru(-tape)PtCl2](PF6)(2) {[6](PF6)(2)}, respectively were also prepared. The molecular structures of the complex cations [2](4+) and [4](4+) were discussed on the basis of the X-ray structures of [2](ClO4)(4)MeCN and [4](ClO4)(4)MeCN. The electrochemical behavior and the UV/Vis absorption spectra of the heterodinuclear tape ruthenium(II) complexes were explored and compared with the data of the analogous mono- and homodinuclear ruthenium(II) complexes of the tape bridging ligand. KW - N ligands KW - Ruthenium KW - Structure elucidation KW - Charge transfer KW - Electrochemistry Y1 - 2016 U6 - https://doi.org/10.1002/zaac.201500645 SN - 0044-2313 SN - 1521-3749 VL - 642 SP - 8 EP - 13 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Brietzke, Thomas Martin A1 - Mickler, Wulfhard A1 - Kelling, Alexandra A1 - Holdt, Hans-Jürgen T1 - Mono- and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes JF - Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry N2 - We report the synthesis of free 1,6,7,12-tetraazaperylene (tape). Tape was obtained from 1,1'-bis-2,7-naphthyridine by potassium promoted cyclization followed by oxidation with air. Mono-and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes of the general formulas [Ru(L-L)(2)(tape)](PF6)(2), [1] (PF6)(2)-[5](PF6)(2), and [{Ru(L-L)(2)}(2)(mu-tape)](PF6)(4), [6](PF6)(4)-[10](PF6)(4), with{L-L = phen, bpy, dmbpy (4,4'-dimethyl-2,2'-bipyridine), dtbbpy (4,4'-ditertbutyl-2,2'-bipyridine) and tmbpy (4,4' 5,5'-tetramethyl-2,2'- bipyridine)}, respectively, were synthesized. The X-ray structures of tape center dot 2CHCl(3) and the mononuclear complexes [Ru(bpy)(2)(tape)](PF6)(2)center dot 0.5CH(3)CN center dot 0.5toluene, [Ru(dmbpy)(2)(tape)] (PF6)(2)center dot 2toluene and [Ru(dtbbpy)(2)(tape)](PF6)(2) center dot 3acetone center dot 0.5H(2)O were solved. The UV-vis absorption spectra and the electrochemical behavior of the ruthenium(II) tape complexes were explored and compared with the data of the analogous dibenzoeilatin (dbneil), 2,2'-bipyrimidine (bpym) and tetrapyrido [3,2-a:2',3'-c:3 '',2''-h:2''',3'''-j] phenazin (tpphz) species. Y1 - 2012 U6 - https://doi.org/10.1039/c2dt11805j SN - 1477-9226 VL - 41 IS - 9 SP - 2788 EP - 2797 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Brietzke, Thomas Martin A1 - Mickler, Wulfhard A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Krüger, Hans-Joerg A1 - Holdt, Hans-Jürgen T1 - Mono- and dinuclear Ruthenium(II)-1,6,7,12-Tetraazaperylene complexes of N,N '-Dimethyl-2,11-diaza[3.3](2,6)-pyridinophane JF - European journal of inorganic chemistry : a journal of ChemPubSoc Europe N2 - Ruthenium(II) complexes [Ru(L-N4Me2)(dape)](PF6)2 {[1](PF6)2}, [Ru(L-N4Me2)(tape)](PF6)2 {[2](PF6)2}, and [{Ru(L-N4Me2)}2(mu-tape)](PF6)4 {[3](PF6)4} were synthesized in two reaction steps by first reacting [Ru(DMSO)4Cl2] with tetraazamacrocyclic ligand N,N'-dimethyl-2,11-diaza[3.3](2,6)-pyridinophane (L-N4Me2) in ethanol under microwave irradiation to the intermediate [Ru(L-N4Me2)Cl2], which was subsequently, without further isolation, reacted with 1,12-diazaperylene (dape) or 1,6,7,12-tetraazaperylene (tape). X-ray structures of [Ru(L-N4Me2)(dape)](PF6)2, [Ru(L-N4Me2)(tape)](PF6)2.acetone, and [{Ru(L-N4Me2)}2(mu-tape)](ClO4)4.MeCN were determined. The UV/Vis absorption spectra of [1](PF6)2, [2](PF6)2, and [3](PF6)4 in acetonitrile display intense low-energy dp(Ru)?p* (dape or tape) MLCT absorption bands centered at 579, 637, and 794 nm, respectively. Reversible metal oxidations for the bimetallic complex [{Ru(L-N4Me2)}2(mu-tape)]4+ ([3]4+) are detected at 1.69 and 1.28 V vs. SCE. The potential difference ?E = 410 mV and the intervalence-charge-transfer (IVCT) transition at 2472 nm indicate a high degree of electronic interaction between the two ruthenium ions mediated through the tape bridging ligand. All three complexes, [1]2+, [2]2+, and [3]4+, were characterized by UV/Vis spectroelectrochemistry. The monooxidized and monoreduced states, [1]3+, [2]3+, [3]5+, and [1]+, [2]+, [3]3+, are accessible by reversible one-electron oxidation and one-electron reduction processes, respectively, as documented by the observation of several stable isosbestic points in the spectral progressions. The second reduction in each complex and the second oxidation in [3]4+ prove to be irreversible in these spectroelectrochemical experiments. Monoreduced species [1]+, [2]+, and [3]3+ yield EPR signals indicating that the unpaired electron is mainly centered on the large surface ligands dape or tape. KW - Ruthenium KW - Macrocyclic li-gands KW - N ligands KW - Redox chemistry KW - Mixed-valent compounds Y1 - 2012 U6 - https://doi.org/10.1002/ejic.201200667 SN - 1434-1948 IS - 29 SP - 4632 EP - 4643 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Cierpiszewski, Ryszard A1 - Rusinska-Roszak, D. A1 - Szymanowski, Jan A1 - Mickler, Wulfhard A1 - Uhlemann, Erhard T1 - Rate of coper extraction and structure of model ß-diketones and 4-acyl-5-pyrazolones Y1 - 1998 ER - TY - GEN A1 - Dosche, Carsten A1 - Mickler, Wulfhard A1 - Löhmannsröben, Hans-Gerd A1 - Agenet, Nicolas A1 - Vollhardt, K. Peter C. T1 - Photoinduced electron transfer in [N]phenylenes N2 - First studies of electron transfer in [N]phenylenes were performed in bimolecular quenching reactions of angular [3]- and triangular [4]phenylene with various electron acceptors. The relation between the quenching rate constants kq and the free energy change of the electron transfer (ΔG0CS ) could be described by the Rehm-Weller equation. From the experimental results, a reorganization energy λ of 0.7 eV was derived. Intramolecular electron transfer reactions were studied in an [N]phenylene bichomophore and a corresponding reference compound. Fluorescence lifetime and quantum yield of the bichromophor display a characteristic dependence on the solvent polarity, whereas the corresponding values of the reference compound remain constant. From the results, a nearly isoenergonic ΔG0CS can be determined. As the triplet quantum yield is nearly independent of the polarity, charge recombination leads to the population of the triplet state. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 23 KW - [N]phenylenes KW - photoinduced electron transfer KW - [N]phenylene dyads Y1 - 2007 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-12463 ER - TY - JOUR A1 - Dosche, Carsten A1 - Mickler, Wulfhard A1 - Löhmannsröben, Hans-Gerd A1 - Agenet, Nicolas A1 - Vollhardt, K. Peter C. T1 - Photoinduced electron transfer in [N]phenylenes N2 - First studies of electron transfer in [N]phenylenes were performed in bimolecular quenching reactions of angular [3]- and triangular [4]phenylene with various electron acceptors. The relation between the quenching rate constants k(q) and the free energy change of the electron transfer (Delta G(CS)(0)) could be described by the Rehm- Weller equation. From the experimental results, a reorganization energy lambda of 0.7 eV was derived. Intramolecular electron transfer reactions were studied in an [N]phenylene bichomophore and a corresponding reference compound. Fluorescence lifetime and quantum yield of the bichromophor display a characteristic dependence on the solvent polarity, whereas the corresponding values of the reference compound remain constant. From the results, a nearly isoenergonic charge separation process can be determined. As the triplet quantum yield is nearly independent of the polarity, charge recombination leads to the population of the triplet state. Y1 - 2007 UR - http://www.sciencedirect.com/science/journal/10106030 U6 - https://doi.org/10.1016/j.jphotochem.2006.12.038 SN - 1010-6030 ER - TY - JOUR A1 - Friedrich, Alwin A1 - Hefele, Heike A1 - Mickler, Wulfhard A1 - Mönner, Anke A1 - Uhlemann, Erhard A1 - Scholz, F. T1 - Voltammetric and potentiometric studies on the stability of vanadium(IV) complexes : a comparision of sulution phase voltammetry with the voltammetry of the microcrystalline solid compounds Y1 - 1998 ER - TY - JOUR A1 - Grobosch, Thomas A1 - Mickler, Wulfhard A1 - Feistel, Lothar A1 - Schilde, Uwe T1 - Separation of arsenic and other heavy metals with impregnated adsorber polymers : chapter 1: synthesis of the impregnation medium and separation of arsenic Y1 - 2006 UR - http://www3.interscience.wiley.com/cgi-bin/jhome/60500203/ U6 - https://doi.org/10.1002/cite.200500170 SN - 0009-286X ER - TY - JOUR A1 - Herzschuh, R. A1 - Wenzlawiak, B. A1 - Plaggenborg, L. A1 - Mickler, Wulfhard A1 - Uhlemann, Erhard T1 - The characterization of the active components in commercial ß-diketone-type extractants LIX 54 and MX 80 A Y1 - 1992 ER - TY - JOUR A1 - Janiak, Chr. A1 - Scharmann, T. G. A1 - Green, J. C. A1 - Parkin, R. P. G. A1 - Kolm, M. J. A1 - Riedel, E. A1 - Mickler, Wulfhard A1 - Elguero, J. A1 - Claramunt, R. M. A1 - Sanz, D. T1 - Effects of nitrogen substitution in Poly(pyrazolyl)borato Ligands : from orbital energy levels to C-H...O Hydrogen Bonding Y1 - 1996 ER - TY - JOUR A1 - Kammer, Stefan A1 - Kelling, Alexandra A1 - Baier, Heiko A1 - Mickler, Wulfhard A1 - Dosche, Carsten A1 - Rurack, Knut A1 - Kapp, Andreas A1 - Lisdat, Fred A1 - Holdt, Hans-Jürgen T1 - 2,11-dialkylated 1,12-diazaperylene copper(I) complexes : first supramolecular column assemblies by pi-pi stacking between homoleptic tetrahedral metal complexes, exhibiting low-energy MLCT transitions N2 - 2,11-Dialkylated 1,12-diazaperylenes (alkyl = Me, Et, iPr) dmedap, detdap and dipdap have been synthesized by reductive cyclization of 3,3-dialkylated 1,1-biisoquinolines 3a-c, resulting in the first copper(I) complexes of a large- surface ligand. The new copper(I) complexes show low-energy MLCT absorptions unprecedented for bis(-diimin)copper(I) complexes. The solid structures of the complexes[Cu(dipdap)2]BF4·CH2Cl2·1.5H2O, [Cu(dipdap)2]OTf·CH2Cl2, [Cu(dipdap)2]I·C2H4Cl2·THF·2H2O, [Cu(dmedap)2]OTf and [Cu(dipdap)2]AQSO3·H2O (AQSO3 = sodium 9,10-dihydro-9,10-dioxo-2- anthracenesulfonate) are reported. In [Cu(dipdap)2]BF4·CH2Cl2·1.5H2O, each copper(I) complex cation interacts with two others by - stacking interactions forming a novel supramolecular column structural motif running along the crystallographic c axis. In the crystalline compound [Cu(dipdap)2]AQSO3·H2O, aggregation between two complex cations and two additional anions by - stacking interactions is observed, leading to a tetrameric assembly. Furthermore, the three complex compounds [Cu(L)2]BF4 (L = dmedap, detdap, dipdap) were tested for sensory applications in aqueous buffer solutions in electrochemical studies of the complex immobilized on glassy carbon electrodes. Y1 - 2009 UR - http://www3.interscience.wiley.com/journal/27721/home U6 - https://doi.org/10.1002/ejic.200900695 SN - 1434-1948 ER - TY - JOUR A1 - Kammer, Stefan A1 - Müller, Holger A1 - Grunwald, Nicolas A1 - Bellin, Anja A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Mickler, Wulfhard A1 - Dosche, Carsten A1 - Holdt, Hans-Jürgen T1 - Supramolecular assemblies with honeycomb structures by pi-pi stacking of octahedral metal complexes of 1,12- diazaperylene N2 - Homoleptic Ni-II and Fe-II complexes of the "large-surface" phenanthroline-type ligand 1,12-diazaperylene (dap), [Ni(dap)(3)](BF4)(2) (1) and [Fe(dap)(3)](PF6)(2) (2), respectively, were synthesized. In the crystal structure the complex cation [M(dap)(3)](2+) (M = Ni, Fe) exhibits C-3 symmetry and interacts with three other cations by pi-pi stacking. It forms a new metalla-supramolecular assembly with a honeycomb structure containing nanochannels running parallel to the crystallographic c axis. Aggregation by pi-pi stacking between metal complexes of "large-surface" ligands should give new perspectives for inorganic supramolecular chemistry. Y1 - 2006 UR - http://www3.interscience.wiley.com/cgi-bin/jhome/27721/ U6 - https://doi.org/10.1002/ejic.200600092 SN - 1343-1948 ER - TY - JOUR A1 - Kammer, Stefan A1 - Starke, Ines A1 - Pietrucha, Andreas A1 - Kelling, Alexandra A1 - Mickler, Wulfhard A1 - Schilde, Uwe A1 - Dosche, Carsten A1 - Kleinpeter, Erich A1 - Holdt, Hans-Jürgen T1 - 1,12-Diazaperylene and 2,11-dialkylated-1,12-diazaperylene iridium(III) complexes [Ir((CN)-N-boolean AND)(2)((NN)-N-boolean AND)]PF6: new supramolecular assemblies JF - Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry N2 - A series of new monocationic iridium(III) complexes [Ir((CN)-N-boolean AND)(2)((NN)-N-boolean AND)]PF6 with "large-surface" alpha,alpha'-diimin ligands (NN)-N-boolean AND (dap = 1,12-diazaperylene, dmedap = 2,11-dimethyl-1,12-diazaperylene, dipdap = 2,11-diisopropyl-1,12-diazaperylene) and different cyclometalating ligands (CN)-N-boolean AND (piq = 1-phenylisoquinoline, bzq = benzo[h]quinoline, ppz = 1-phenylpyrazole, thpy = 2-(2-thienyl)pyridine, ppy = 2-phenylpyridine, meppy = 2-(4-methylphenyl)pyridine, dfppy = 2-(2,4-difluorophenyl)pyridine) were synthesized. The solid structures of the complexes [Ir(piq)(2)(dap)]PF6, [Ir(bzq)(2)(dap)]PF6, [Ir(ppy)(2)(dipdap)]PF6, [Ir(piq)(2)(dmedap)]PF6, [Ir(ppy)(2)(dap)]PF6 and [Ir(ppz)(2)(dap)]PF6 are reported. In [Ir(piq)(2)(dap)]PF6, the dap ligand and one of the piq ligands of each cationic complex are involved in pi-pi stacking interactions forming supramolecular channels running along the crystallographic c axis. In the crystalline [Ir(bzq)(2)(dap)]PF6 pi-pi stacking interactions between the metal complexes lead to the formation of a 2D layer structure. In addition, CH-pi interactions were found in all compounds, which are what stabilizes the solid structure. In particular, a significant number of them were found in [Ir(piq)(2)(dap)]PF6 and [Ir(bzq)(2)(dap)]PF6. The crystal structures of [Ir(ppy)(2)(dipdap)]PF6 and [Ir(ppy)(2)(dmedap)]PF6 are also presented, being the first examples of bis-cyclometalated iridium(III) complexes with phenanthroline-type alpha,alpha'-diimin ligands bearing bulky alkyl groups in the neighbourhood of the N-donor atoms. These ligands implicate a distorted octahedral coordination geometry that in turn destabilized the Ir-N-N boolean AND N bonds. The new iridium (III) complexes are not luminescent. All compounds show an electrochemically irreversible anodic peak between 1.15 and 1.58 V, which is influenced by the different cyclometalated ligands. All of the new complexes show two reversible successive one-electron "large-surface" ligand-centred reductions around -0.70 V and -1.30 V. Electrospray ionisation mass spectrometry (ESI-MS) and collision induced decomposition (CID) measurements were used to investigate the stability of the new complexes. Thereby, the stability agreed well with the order of the Ir-N-N boolean AND N bond lengths. Y1 - 2012 U6 - https://doi.org/10.1039/c2dt30412k SN - 1477-9226 VL - 41 IS - 34 SP - 10219 EP - 10227 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Mickler, Wulfhard T1 - Separation of metals by liquid-liquid-extraction with ß-diketones and 4-acyl-5-pyrazolones from different complex-forming medias Y1 - 1996 ER - TY - JOUR A1 - Mickler, Wulfhard T1 - Liquid-liquid-extraction of copper from ammoniacal solution with 4-acylpyrazol-5-ones and ß-diketones Y1 - 1993 SN - 1-85861-042-7 ER - TY - JOUR A1 - Mickler, Wulfhard T1 - Separation of heavy metals from landfill leachate by reactive liquid-liquid-extraction N2 - Based on a study of the German Ministry of Research and Technology in 1990 every year about 2.5 t of heavy metals are released per hectare of landfill by aqueous leaching. This leachate contains approximately 2000 t of heavy metals per year. Their decontaminations in accordance with the legal requirements represent an enormous potential for easing the burden on the environment. On the other hand, this potential opens new possibilities in the production and recycling of selected compounds. The composition of a given model solution corresponds to a landfill leachate resulting from a municipal dump leachate produced by an average German city. Actually, in most cases, a decontamination of such solutions occurs by the transfer of the problematic cations into insoluble compounds usually done by precipitation. The result of the procedure is an unspecific separation of all liquid components - and the "cycle of waste" (landfill- leaching-deposition) begins anew, certainly on a higher level. The objective of our work is the simultaneous separation of heavy metals from alkaline earth metals and iron in order to obtain a leachate which we can lead back to the landfill. The reactive extraction as a separation process offers the possibility of a selective separation of cations that is the separation of toxic - from unproblematic components and includes also the possibility of electrolysis or further winning processes to obtain the wished metals. For the realisation of extraction processes, several commercial extractants and technical equipments are available. Apart from iron, LIX 54 could be used advantageously for an extraction process - unfortunately without any considerable extraction of cadmium. But it is favourable to separate non toxic alkaline earth metals from problematic heavy metals. Such a complex task as the separation of cations from natural solutions cannot be solved easily in a one-step-extraction process. Better results should be obtained by the combination of different procedures, e.g. extraction, ion-exchange and precipitation. Y1 - 2001 ER - TY - JOUR A1 - Mickler, Wulfhard T1 - Reactive Liquid-liqudi-extraction of heavy metals from landfill leachates N2 - Toxic heavy metals are extracted simultaneously by reactive liquid-liquid-extraction from a model landfill leachate. This is taken as an example to generate an unproblematic waste water. Alkylphosphoric acids (commercial D2EHPA and D2EHTPA), ß-diketones, 4-Acyl-5-pyrazolones and a novel commercial alkyl-methyl-phosphonic acid are used as extractants. By means of the functions E%=f (pH, t) and lg D=f (pH, cL) some thermodynamic parameters of the extraction are determined. In the case of the alkylthiophosphoric acid the thiophilic cations are extracted advantageously in contrast to chromium, magnesium or calcium. There is no significant separation between the heavy metals and the alkaline earth metals. The complexes are extracted with the composition ML(HL)n. According to their ligand force, the presence of complexing agents in the aqueous phase (for example cyanide, tartrate, ammonia or chloride) hinders the extraction. The influence of humic acid is comparable to that of tartaric acid. Because of the formation of less soluble compounds, sulphate ions make the extraction of calcium more difficult. The extraction data points out that aromatic or chloric solvents are not advantageous in contrast to the non toxic aliphatic hydrocarbons. With the novel aminomethylphosphonic acid (ironex, BASF) the extraction of iron, indium and gallium is possible at a pH > 1.5 as ML2(HL) and ML(HL)2 resp. Copper and zinc were extracted quantitatively as 1:2 complexes only in a small pH-range between 4 to 6. Generally, the best results were found for the ß-diketones (LIX 54 included) and 4-acyl-5-pyrazolones. In these cases the toxic heavy metals could be separated quantitatively. Only 6% of calcium and 23% of magnesium are coextracted by the ligands. The extraction process can further be optimized by synergistic effects. Y1 - 2001 ER -