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  • Chemistry  (17)
  • Inorganic Chemistry  (13)
  • Cobalt (nickel) complexes
  • Bis(1, 3-diketonato)cobalt-bisimidazoles
  • [Li(TMED)2][Co(COD)2]
  • Wiley-Blackwell  (17)
  • 1980-1984  (17)
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  • Wiley-Blackwell  (17)
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 479 (1981), S. 147-157 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1-Bis(carboxymethyl)amino-butanedione-2,3-dioxime as an Ambifunctional Ligand in Complexes of 3d ElementsIn acid solution 1-bis(carboxymethyl)amino-butanedione-2,3-dioxime H4A affords octahedral 1,1 complexes MII(H2A)(H2O)x (MII = Cu, Ni, Co) coordinating as a tetradentate ligand by the imino diacetic acid group and the oxime group in 2-position. At 4.5 〈 pH 〈 8 Ni(H2A)(H2O)x and Cu(H2A)(H2O)x are deprotonated, in addition to Ni(HA)- the binuclear chelate [Ni2(HA)2]2- is formed. In solution containing a surplus of ligand H4A also the planar chelate [Ni(HA)2]4- with the donor set N4 can be detected. The transition from [Ni(HA)]- to [Ni(HA)2]4- is connected with a change of the coordination sphere (imino diacetic acid group → dioxime group) and the cis-trans isomerization of at least one oxime group.Protonation and stability constants are given and the properties of solid complexes are described.
    Notes: 1-Bis(carboxymethyl)amino-butandion-2,3-dioxim H4A bildet in saurer Lösung oktaedrische 1,1-Komplexe MII(H2A)(H2O)x (MII = Cu, Mi, Co), in denen es vierzählig über die Iminodiessigsäure- und die Oximgruppe in 2-Stellung koordiniert. Ni(H2A)(H2O)x und Cu(H2A) (H2O) unterliegen im neutralen Gebiet der Deprotonierung; im Falle des Nickel(II) entsteht neben Ni(HA)- auch das binucleare Chelat [Ni2(HA)2]2-. In Lösungen mit einem Ligandenüberschuß kann der planare Komplex [Ni(HA)2]4- mit dem Donatorsatz N4 nachgewiesen werden. Beim übergang von [Ni(HA)]- in [Ni(HA)2]4- wechselt das Nickel(II) die Koordinationssphäre; gleichzeitig erfolgt die Cis-trans-Isomerisierung mindestens einer Oximgruppe.Protonierungs- und Komplexstabilitätskonstanten sowie die Eigenschaften kristalliner Komplexe werden mitgeteilt.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 477 (1981), S. 167-177 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Oxidation of Mixed Ligand Nickel(0) Complexes by Organic HalidesThe oxidation of (dipy)Ni(PPh3)2 by alkyl and aryl iodides or bromides affords the nickel(I) complexes (dipy)Ni(PPh3)X (X = Br, I). No normal products of oxidative addition are obtained. But in the case of methyl and ethyl halides complexes of the type (dipy)NiR2 are formed as intermediates. Basing on the identified final products and on the correalation between the reactivity of the organic halides and their polarographic half wave potentials a mechanism of the reaction is proposed. The first step is a charge transfer from nickel(0) to the organic halide.Further synthesis, reactions, and the ESR-spectra of the complexes (dipy)Ni(PPh3)X and a synthesis of (dipy)Ni(CH2Ph)2 are described. Experiments to prepare pure (dipy)Ni(PPh3)Cl had no success.
    Notes: (dipy)Ni(PPh3)2 wird von Alkyl- und Aryliodiden bzw. -bromiden zu den Nickel(I)-Verbindungen (dipy Ni(PPh3)X (X = I, Br) oxydiert. Normale Produkte der oxidativen Addition werden nicht gefunden. Im Falle der Methyl- bzw. Ethylhalogenide entstehen jedoch Komplexe des Typs dipy)NiR2 als Intermediate. Auf Grund der identifizierten Endprodukte und der Zusammenhänge zwischen der Reaktivität der organischen Halogenide und ihrer polarographischen Halbstufenpotentiale wird ein Reaktionsmechanismus vorgeschlagen, an dessen Anfang ein Chargetransfer vom Nickel(0)-Komplex zum organischen Halogenid steht.Es werden weitere Synthesemöglichkeiten, Reaktionen und die ESR-Spektren der Komplexe (dipy)Ni(PPh3)X sowie die Synthese von (dipy)Ni(CH2Ph)2 mitgeteilt. Die Darstellung von reinem (dipy)Ni(PPh3)Cl gelang nicht.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 492 (1982), S. 52-62 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Behaviour of Cobalt(II) and Iron(III) in Case of Liquid-liquid Extraction by Pyridyl Substituted Benzene SulfonamidesPyridyl substituted benzene sulfonamides N 3 NHSO2R and N 2 NHSO2R which may be used as models of sulfonamide based metal extractants (LIX 34 et. al.) were studied as to their coordinative behaviour towards cobalt(II) and iron(III).The structure of Co(N 3 NSO2R)2 is distorted tetrahedral. Considering bond lengths and angles π-backdonation between cobalt and the nitrogen atoms is indicated which creates a higher effective charge on the central atom than in normal cobalt(II) complexes. Therefore, when observing normal conditions, Co(N 3 NSO2R)2 is not oxidized but reduced. Co(N 2 NSO2R)2 is a sulfonamide bridged tetramer with pentacoordinate cobalt(II).Iron(III) forms the low-spin complex salts [Fe(N 3 NHSO2R)2 (N 3 NSO2R)](NO3)2 · xH2O and [Fe(N 2 NHSO2R)2(N 2 NSO2R)](NO3)2 · xH2O which are insoluble in organic solvents. This is the reason why the copper(II)-iron(III) separation by sulfonamide based metal extractants proceeds without problems.
    Notes: Als Modelle für die in der Patentliteratur empfohlenen Metallextraktionsmittel auf Sulfonamidbasis (LIX 34 u.a.) werden pyridylsubstituierte Benzensulfonamide N 3 NHSO2R und N 2 NHSO2R auf ihr komplexchemisches Verhalten gegenüber Cobalt(II) und Eisen(III) untersucht.Co(N 3 NSO2R)2 hat eine stark verzerrte tetraedrische Struktur. Auf Grund der Strukturdaten wird eine π-Rückgabebindung vom Cobalt zum Amidstickstoff diskutiert, die eine gegenüber normalen Cobalt(II)-Komplexen erhöhte effektive Ladung des Zentralatoms erzeugt. Deshalb gelingt es unter normalen Bedingungen nicht, Co(N 3 NSO2R)2 zu oxidieren, wohl aber zu reduzieren. Co(N 2 NSO2R)2 ist tetramer, über Sulfonamidbrücken wird die Koordinationszahl 5 erreicht.Eisen(III) bildet die Komplexsalze [Fe(N 3 NHSO2R)2(N 3 NSO2R)](NO3)2 · xH2O und [Fe(N 2 NHSO2R)2(N 2 NSO2R)](NO3)2 · xH2O, die zum Low-Spin-Typ gehören und in organischen Lösungsmitteln nicht löslich sind. Darin liegt die Erklärung für den Befund, daß im Falle der Metallextraktionsmittel auf Sulfonamidbasis die Kupfer(II)-Eisen(III)-Trennung keine Probleme bringt.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 465 (1980), S. 141-146 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Cyclic Carbonic Acid Anhydrides with (α,α′-Dipyridyl)-(Cyclooctadiene-1,5) NickelWith maleic anhydride (dipy)Ni(COD) reacts by substitution forming (dipy)Ni(MSA)2 (I) and (dipy)Ni(MSA) (II). While in I the bonding of MSA occurs only by the C = C group, in II MSA coordinates additionally by one of the carbonyl functions. With phthalic anhydride (PSA) and succinic anhydride (dipy)Ni(COD) by a redox addition gives six membered metalacycles V and VII, which are decarbonylated at higher temperatures producing the five-membered metalacycles VI and VIII. The IR spectra of the new compounds are discussed.
    Notes: (dipy)Ni(COD) reagiert mit Maleinsäureanhydrid (MSA) unter Substitution zu (dipy)Ni(MSA)2 (I) und (dipy)Ni(MSA) (II). Während in I die Bindung nur über die C = C-Gruppe erfolgt, Koordiniert MSA in II zusätzlich über eine Carbonylfunktion. Mit Phthalsäureanhydrid (PSA) und Bernsteinsäureanhydrid (BSA) ergibt (dipy)Ni(COD) im Zuge einer Redox-addition Sechsgliedrige Metallacyclen V und VII, die bei erhöhter Temperatur unter Decarbonylierung in die fünfgliedrigen Metallacyclen VI bzw. VIII übergehen. Die IR-Spektren der neuen Verbindungen werden diskutiert.
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  • 15
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Substituted 2-(Thiazol-4-yl)-phenols as Ligands and Potential Extractants for Copper (II)Substituted 2-(thiazol-4-yl)-phenols are obtained by the HANTZSCH synthesis. Their solubility in toluene is higher than in n-octane depending on the position, the chain length, and the polarity of the substituents. From alcoholic solutions complexes of the type CuL2n are precipitated. According to the substituents their structure is distorted octahedral (CuL22, CuL23) or distorted tetrahedral (CuL28, CuL29). The new complexes are nearly insoluble in toluene and aliphatic hydrocarbons, but CuL28 and CuL29 are soluble in chloroform. Therefore copper(II) may be extracted by HL8 and HL9 using chloroform as a diluent.
    Notes: Durch die HANTZSCHsche Synthese werden substituierte 2-(Thiazol-4-yl)-phenole HLn hergestellt. Ihre Löslichkeit ist in Toluen besser als in n-Octan und hängt von der Stellung, der Kettenlänge und der Polarität der Substituenten ab. Aus alkoholischen Lösungen kristallisieren Komplexe des Typs CuL2n. Je nach den Substituenten ist ihre Struktur verzerrt oktaedrisch (CuL22, CuL23) oder verzerrt tetraedrisch (CuL28, CuL29). Alle neu dargestellten Kupfer(II)-Komplexe sind in Toluen und aliphatischen Kohlenwasserstoffen schwer löslich. Dagegen lösen sich die Verbindungen CuL28 und CuL29 gut in Chloroform. Kupfer(II) kann daher mit HL8 und HL9 in Chloroform als Verdünnungsmittel extrahiert werden.
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 323 (1981), S. 1013-1013 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 325 (1983), S. 211-224 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Coordinative Behaviour of N-Substituted 2-(Δ2-Imidazolin-2-yl)-phenols as Metal ExtractantsN-Substituted 2-(Δ2-imidazolin-2-yl)-phenols (R4NNOH) are obtained by the reaction of N-alkyl diaminoethane-1, 2 and 2-hydroxybenzoic acid esters. In contrast to many other copper(II) complexes with the donor set N2O22-(A), the species Cu(R4NNO)2(B) are easily soluble in nonpolar solvents. The reason is the monomeric square-planar structure of B, which differs from the polymeric distorted octahedral structure of A.The two maxima in the vis-spectra of Cu(R4NNO)2 and Ni(R4NNO)2 are assigned to the 3 dxy → 3 dx2-y2 and the 3 dxz, 3 dyz → 3 dx2-y2 electron transitions. The shift of these maxima, which is connected with the dissolution in chloroform, is explained by the formation of hydrogen bonds between the solvent and the N-alkylated nitrogen atoms of the ligands.1H-n. m. r.-spectra and solubility of the ligands and the crystal structure of Cu[(C4H9)NNO]2 are described.
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