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  • Inorganic Chemistry  (13)
  • Polymer and Materials Science  (1)
  • Nickel complexes
  • Thermochemistry
  • preparation
  • Bis(1, 3-diketonato)cobalt-bisimidazoles
  • [Li(TMED)2][Co(COD)2]
  • Wiley-Blackwell  (14)
  • 1980-1984  (14)
Collection
Keywords
  • Inorganic Chemistry  (13)
  • Polymer and Materials Science  (1)
  • Nickel complexes
  • Thermochemistry
  • preparation
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  • Wiley-Blackwell  (14)
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Year
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 17 (1983), S. 931-943 
    ISSN: 0021-9304
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: A study using an electro-osmotic cell suitable for actuating an implantable insulin micropump showed that controlled variable flow rates in the order of 0.2 mL/day are possible. The cell functioned continuously with low energy and power requirements and long service life. The principle of operation is compatible with achieving the very low flow rates necessary if highly concentrated insulin is to be used to avoid frequent insulin reservoir refilling. An electro-osmotic cell, Ag/ AgCl/NaCl(aq)/ cation exchange membrane/NaCl(aq)/ AgCl/ Ag, was connected to a constant current power supply which reversed the direction of the current every 10 mins causing a to-and-fro transport of fluid through the membrane. Flow rates of 0.15-0.60 μL/min were achieved with currents of 2.5-10 mA. At the low flow rate, energy consumption was 6.4 × 10-2 J/μL and peak power requirement was 〈2.0 × 10-4 W. Fluid was transported against a pressure gradient of 52 cm Hg. The cell contained a total electrolyte volume of 〈0.25 mL. The membrane showed no change in properties after 10,000 current reversals (69 days). To function as an actuator for an implantable insulin micropump, the electro-osmotic cell requires a switching and valving assembly; a suitable design for this is briefly considered.
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  • 2
    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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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 489 (1982), S. 67-76 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Mixed Ligand Complexes of Nickel(0) with Carbon DichalcogenidesDecisive for the occurrence of a reaction between mixed ligand complexes of nickel(0) and carbon dichalcogenides is the HOMO-energy of the complex and the LUMO-energy of the reagent, which are reflected in the corresponding polarographic half-wave potentials. Therefore, (dipy)-Ni(COD) is substituted by SeCS, CS2 and SCO, whereas (PPh3)2Ni(C2H4) only reacts with CS2, but not with SCO. Substitution by CO2 needs substrates like Ni(PCy3)3 or Ni(PEt3)4 which have the lowest anodic waves.(PCy3)2Ni(C2H4) and (dipy)Ni(PPh3)2 effect C=S-bond breaking in SCO, and mixed carbonyls, such as (PCy3)2Ni(CO)2 or (PPh3)2Ni(CO)2, are formed. Futher products are dithiocarbonates or oligonuclear nickel sulfides which are stabilized by a phosphine.Another oligonuclear complex, (PPh3)2Ni3(CS2)2, is formed by the reaction of CS2 with surplus (PPh3)2Ni(C2H4). The function of CS2 is that of a bridging ligand.The carbon dichalcogenides are side-on (η2) coordinated in compounds like (dipy)Ni(CS2), (PPh3)Ni(CS2) and (dipy)Ni(SCO). It is always the highest electronegative heteroatom of the non symmetric ligands SeCS and SCO which does not interact with the central atom.
    Notes: Über das Eintreten einer Reaktion von Gemischtligand-Komplexen des Nickel(0) mit Kohlenstoffdichalcogeniden entscheiden die HOMO-Energie des Komplexes und die LUMO-Energie des Reagenzes, die sich in den entsprechenden polarographischen Halbstufenpotentialen widerspiegeln. (dipy)Ni(COD) reagiert daher mit SeCS, CS2 und SCO unter Substitution, (PPh3)2Ni(C2H4) nur mit CS2, nicht jedoch mit SCO. Mit CO2 setzen sich nur Ni(PCy3)3 und Ni(PEt3)4 als die Komplexe mit den niedrigsten anodischen Stufen um.An (PCy3)2Ni(C2H4) und (dipy)Ni(PPh3)2 wird die C=S-Bindung von SCO gespalten. Dabei entstehen die ternären Carbonyle (PCy3)2Ni(CO)2 bzw. (PPh3)2Ni(CO)2. Der elimierte Schwefel bildet ein phosphinsubstituiertes oligonukleares Nickelsulfid bzw. ein Dithiocarbonat.Ein oligonuklearer Komplex, (PPh3)2Ni3(CS2)2, ist das Produkt der Umsetzung von (PPh3)2Ni(C2H4) mit CS2 im Unterschuß. CS2 fungiert in diesem Fall als Brückenligand.In den Komplexen (dipy)Ni(CS2), (PPh3)Ni(CS2), (dipy)Ni(SCO) sind die Kohlendichalcogenide „side-on“ (η2-) koordiniert. Bei den unsymmetrischen Liganden SeCS und SCO bleiben die am stärksten elektronegativen Heteroatome von der Wechselwirkung mit dem Zentralatom ausgeschlossen.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 490 (1982), S. 147-152 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Liquid-Liquid Extraction of Metals with Some Tetradentate Schiff BasesThe liquid-liquid extraction of copper(II), iron(III), nickel(II), cobalt(II), and zinc(II) with some tetradentate Schiff bases HO∩N∩N∩OH has been investigated. The extraction is strongly influenced by changing the size of the chelate ring. From slope analysis, the extracted species are found to be neutral complexes MII (O∩N∩N∩O) in the case of bivalent metal ions. Iron(III) forms chloride containing complexes in the organic phase. The complex behaviour of these Schiff bases in the solid state has been compared with the complex formation in solution.
    Notes: Es wird über die Flüssig-Flüssig-Extraktion von Kupfer(II), Eisen(III), Nickel(II), Cobalt(II) und Zink(II) mit vierzähligen Schiffschen Basen HO∩N∩N∩OH berichtet. Der Extraktionsvorgang hängt stark von der Gestalt der gebildeten tricyclischen Komplexe ab. Im Falle der zweiwertigen Metallionen werden, wie die Slope-Analyse zeigt, die Chelate MII (O∩N∩N∩O) extrahiert. Eisen(III) bildet in der organischen Phase chloridhaltige Komplexe. Die Komplexbildung der Schiffschen Basen in Lösung wird mit der im festen Zustand verglichen.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 504 (1983), S. 105-112 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polyamino Alcohols as Bifunctional Extractants for Copper(II)Polyamino alcohols obtained by the addition of mono- or bifunctional epoxides to disecondary diamines are studied with regard to their applicability to copper(II) extraction. The simple diamino diols IV, V, and VI proved to be inefficient. But, depending on the anion, distribution ratios D up to 1000 were measured with the polyamino alcohol III (chloroform as a diluent) in weakly acidic solution. This is a result of the special structure of the copper(II) complex of III which is both a metal chelate and a substituted ammonium salt. The ammonium part, because of its high affinity to the chloroform phase, has the function of a phase-transfer reagent of the chelate part.
    Notes: Polyaminoalkohole, die durch Addition von mono- oder bifunktionellen Epoxiden an disekundäre Diamine entstehen, werden auf ihre Verwendbarkeit als Extraktionsmittel für Kupfer(II) geprüft. Während sich die einfachen Diaminodiole IV bis VI als ungeeignet erweisen, werden mit dem Polyaminoalkohol III (Verdünnungsmittel Chloroform) abhängig vom Anion in schwach saurer Lösung maximale Verteilungsverhältnisse D von 1000 gefunden. Dieser Effekt geht auf den besonderen Charakter der Kupfer(II)-Komplexe von III zurück, die die Funktion eines Metallchelates und eines substituierten Ammoniumsalzes in sich vereinigen. Der Ammoniumteil mit seiner hohen Affinität für die Chloroformphase wirkt als Phasentransfer-Reagenz für den Chelatteil.
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  • 6
    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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  • 7
    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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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 510 (1984), S. 11-15 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Benzyl Nickel(II) Complexes and their ReactionsBy the oxydative addition of p-substituted benzyl chlorides to (Ph3P)2Ni(C2H4) at -20°C the violet nickel(II) complexes (Ph3P)2Ni(p-CH2C6H4R)Cl (R = CN, COOH, CH3, Cl) are, formed. In water containing solutions the carbonic acid (Ph3P)2Ni(p-CH2C6H4COOH)Cl is rearranged to the corresponding p-methylbenzoate.With carbon dioxide the complexes (Ph3P)2Ni(p—CH2C6H4R)Cl react like Grignard compounds. Diphenyl ethine and butadien-1,3 are inserted in the Ni - C bond at room temperature. Substituted nickel-σ-vinyl or π-allyl complexes are obtained. The reactivity of the nickel-σ-benzyl compounds is compared with that of other nickel(II)-alkyl compounds.
    Notes: Die oxydative Addition von p-substituierten Benzylchloriden an (Ph3P)2—Ni(C2H4) bei -20°C ergibt die violetten Nickel(II)-Komplexe (Ph3P)2Ni(p—CH2C6H4R)Cl (R = CN, COOH, CH3, Cl). Die Carbonsäure (Ph3P)2Ni(p—CH2C6H4COOH)Cl lagert sich in Gegenwart von Wasser in das entsprechende p-Methylbenzoat ein.Die Verbindungen des Typs (Ph3P)2Ni(p—CH2C6H4R)Cl reagieren mit Kohlendioxid grignardanalog. Diphenylethin und Butadien-1,3 werden bei normaler Temperatur in die Ni - C-Bindung eingeschoben. Dabei entstehen substituierte Nickel-σ-vinyl- bzw. π-allyl-Komplexe. Das Reaktionsverhalten der Nickel-σ-benzylverbindungen wird mit dem anderer Nickel(II)-alkylverbindungen verglichen.
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  • 9
    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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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 468 (1980), S. 153-164 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation and Reactions of Nickel(II) Complexes of Amine Substituted 1,2-DioximesIn solution nickel(II) with amine substituted 1,2-dioximes R2NDH2 forms neutral complexes Ni(R2NDH)2 ans cations [Ni(R2NHDH)2]2+ or (Ni(R2NDH)(R2NHDH)+. Well-crystallized salts are only obtained of the cations [Ni(R2NDH)2]2+ and anions like ClO4- and BPH4-. A red and an Orange isomere isomere of Ni(Me2NDH)2 are isolated. The reactions of the neutral species Ni(R2NDH)2 with BF3 or BEt3 yield the macrocyclic compounds [NiR2NHDBF2)2](BF4)2 or Ni(R2NDBEt2)2. Paramagnetic pyridine adducts are formed by the salts [Ni(R2NHDH)2](ClO4)2.On account of their colours and their chemical reactions the new complexes are classified into two groups differing by the stack of the individual, planar molecules in the crystal. The interdependence between the structure of the planar molecules and their stack in the crystal is discussed. The isomeres of Ni(Me2NDH)2 are assigned to different groups.
    Notes: Nickel(II) bildet in Lösung mit aminsubstituierten 1,2-Dioximen R2NDH2 Neutralkomplexe Ni(R2NDH)2 und Kationen [Ni(R2NHDH)2]2+ bzw. [Ni(R2NDH)(R2NHDH)]+. Nur die Kationen [Ni(R2NHDH)2]2+ ergeben mit Anionen wie ClO4- und BPH4 gut kristallisierende Salze. Die Reaktionen der Neutralkomplexe Ni(R2NDH)2 mit BF3 bzw. BEt3 führt zu den Makrocyclen [Ni(R2NHDBF2)2] (BF4)2 bzw. Ni(R2NDBEt2)2. Die Isolierung fester paramagnetischer Pyridinaddukte gelang im Fall der komplexen Salze [Ni(R2NHDH)2](ClO4)2.Auf Grund der Farbe und der chemischen Reaktionen werden die neuen Komplexe in zwei Gruppen eingeteilt, die sich in der Stapelfolge der planaren Einzelmoleküle Unterscheiden. Es werden die Zusammenhänge zwischen der Struktur der Einzelmoleküle und der Art der Stapelung im Kristall diskutiert. Die Isomeren des Ni(Me2NDH)2 (rot und gelb) gehören unterschiedlichen Gruppen an.
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