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  • 1985-1989  (9)
  • Chemistry  (9)
  • EPR, X-Ray
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  • 1
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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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: Dithiazolium Salts of Halometalates - Synthesis and Structure of 3-Diethylamino-5-phenyl-1,2,4-dithiazolium-tetrachloroniccolate (II)Chlorination of NiII-coordinated 1,1-diethyl-3-benzoyl-thiourea by SOCl2 in acetonitrile yields turquoise 3-diethyl-amino-5-phenyl-1,2,4-dithiazolium-tetrachloroniccolate. Its reduction produces cis-bis-(1,1-diethyl-3-thiobenzoylthioureato)nickel(II). The mechanism of formation as well as the crystal and molecular structure of the title compound are presented.
    Notes: Die Chlorierung von an NiII innerkomplex gebundenem 1,1-Diethyl-3-benzoylthioharnstoff mittels SOCl2 führt in Acetonitril zu türkisem 3-Diethylamino-5-phenyl-1,2,4-dithiazolium-tetrachloroniccolat, aus dem durch Reduktion cis-Bis-(1,1-diethyl-3-thiobenzoyl-thioureato)nickel(II) zugänglich ist. Der Bildungsmechanismus des Dithiazoliumsalzes wird erörtert und die Kristall- und Molekülstrukturanalyse vorgestellt.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Coordination Chemistry of 1,3-Dithiole-2-thione-4,5-diselenolate (dsit)  -  Comparison with 1,3-Dithiole-2-thione-4,5-dithiolate (dmit)Synthesis and properties of metal(II) and/or metal(III) bis-chelates of 1,3-dithiole-2-thione-4,5-diselenolate (dsit) of general type (Bu4N)n[M(dsit)2] (n = 2: M = Zn, Cd, Hg, Cu, Ni, Pd, Pt; n = 1: M = Ni, Au) are described. By comparison of the ir, 13C nmr, epr spectra, cyclovoltammetric data, and x-ray investigations (nickel-bis-chelates) of chelates of dsit and those of the chelates of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) the consequences of selenium for sulfur substitution on position 4 and 5 of the heterocyclic ligand are discussed.
    Notes: Synthese und Eigenschaften von Metall(II)- und/oder Metall(III)-Bis-Chelaten des 1,3-Dithiol-2-thion-4,5-diselenolats (dsit) vom Typ (Bu4N)n[M(dsit)2] (n = 2: M = Zn, Cd, Hg, Cu, Ni, Pd, Pt; n = 1: M = Ni, Au) werden beschrieben. Anhand der IR-, 13C-NMR-, EPR-Spektren, Cyclovoltammogramme und röntgenographischen Untersuchungen der Nickel-Bis-Chelate werden die Auswirkungen der Substitution von Schwefel durch Selen an der 4- und 5-Position diskutiert.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of a Novel Trimetallamacrocyle: cyclo-Tri[nickel-μ-[1,1,1′,1′-tetraethyl-3,3′-terephthaloyl-bis-thioureato(2-)-S,O:O′,S′]]The structure of the title compound has been determined by an X-ray structure analysis. The compound crystallizes in the triclinic space group P1 with a = 13.900, b = 15.403, c = 16.615 Å, δ = 84.01, β = 70.61, γ = 89.64° and Z = 2. The solution of the structure was performed by direct methods. The final R value was R = 0.073 for 2824 observed reflections. The molecule has a cyclic structure consisting of three molecules of the quadridentate ligand and three nickel atoms. The formed ring is a 27-membered trimetallamacrocycle. The nickel atoms form a nearly equilateral triangle with distances of 10.25 Å, 10.45 Å and 10.45 Å. The molecule is relatively planar.
    Notes: Die Struktur der Titelverbindung wurde durch Röntgenkristallstrukturanalyse bestimmt. Die Verbindung kristallisiert triklin in der Raumgruppe P1 mit den Gitterkonstanten a = 13,900, b = 15,403, c = 16,615 Å, δ = 84,01, β = 70,61, γ = 89,64° und Z = 2. Die Lösung der Struktur erfolgte mit direkten Methoden. Der abschließende R-Wert betrug R = 0,073 für 2284 beobachtete Reflexe. Das Molekül besitzt eine zyklische Struktur, bestehend aus drei Molekülen des quadridentaten Liganden und drei Nickel-Atomen. Der gebildete Ring ist ein 27gliedriger Trimetallamacrocyclus. Die Nickel-Atome bilden ein nahezu gleichseitiges Dreieck mit Abständen von 10,25 Å, 10,45 Å und 10,45 Å. Das Molekül ist relativ planar.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 537 (1986), S. 133-144 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Binucleating Bis-N-acylthioureas - Ligands in Trimetallamacrocycles and Polynuclear Metal ChelatesBy symmetric linking of two bidentate N-acylthioureas two types of quadridentate bis-N-acylthioureas are available which act - after di-deprotonation - as bis-bidentate S, O ligands towards polyvalent metal ions. They can form oligomeric or polymeric, cyclic or chain chelates. With 1,1,1′,1′-tetraalkyl-3,3′-terephthaloyl-bis-thioureas (H2L) we obtained oligomeric triangulotrimetalla macrocycles Ni3L3 and Cu3L3. They contain perimetric 27-membered rings, counting the internal oxygens, or 39-membered rings with the external sulfur atoms on the other hand, i. e. equal chalcogen atoms are in cis-positions within each chelate unit around the three metal ions. The trimetallamacrocyclic structure was proved by x-ray crystal and molecular structure analysis of Ni3L3 (alkyl = Et) or EPR of the corresponding Cu3L3. Diamin-linked bis-N-acylthioureas form insoluble 1:1 polymeric chelates.
    Notes: Durch geeignete symmetrische Verknüpfung zweier bidentater N-Acylthioharnstoffunktionen sind zwei Typen quadridentater Bis-N-acylthioharnstoffe zugänglich, die gegenüber mehrwertigen Metallionen als bis-bidentate S, O-Liganden fungieren. Sie können oligomere oder polymere, zyklische oder offenkettige Chelate bilden. Mit 1,1,1′,1′-Tetraalkyl-3,3′-terephthaloyl-bis-thioharnstoffen (H2L) erhielten wir oligomere triangulare Trimetallamacrocyclen Ni3L3 und Cu3L3, die perimetrische 27-Ringe mit den internen Sauerstoffligatoren bzw. 39-Ringe mit den externen Schwefelligatoren aufweisen. In jeder Chelateinheit sind die Schwefel- bzw. Sauerstoffatome in cis-Anordnung. Die makrozyklische Struktur wurde mittels RKSA (Ni3L3; Alkyl = Et) bzw. EPR (Cu3L3; Alkyl = Et) bewiesen. Diaminverknüpfte Bis-N-acylthioharnstoffe bilden unlösliche 1:1 Polymerchelate.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electrochemical Reduction of CSSe and CSe2 in Dimethylformamide: Heterocyclic 1,2-Dichalcogenolates and their Coordination ChemistryStarting from carbon diselenide or carbon selenidesulfide the electrochemical preparation (electrosynthesis) of heterocyclic dichalcogenolates C3X52- (X = Se: dsis; X = S/Se: C3SxSey2-) is outlined. The 1,2-dichalcogenolate compounds were isolated and characterized as dibenzoyl derivatives. Bis- or tris-chelates of general type Am[M(C3X5)n] (with A = Bu4N+, Ph4As+; M = ZnII, PtII, PdII, NiIII, CuIII, AuIII, InIII; X = Se, S/Se; m = 1, 2, 3; n = 2, 3, respectively) are available directly from methanolic solutions of the dibenzoylates after hydrolytic cleavage of the latter with sodium methanolate. In addition bis-chelates Bu4N[Ni(C3X5)2] (X = Se, S/Se) have been characterized by cyclovoltammetry and epr spectroscopy and compared with the corresponding all-sulfur ligand compound Bu4N[Ni(dmit)2] (X = S). Arguments are given for the fact that the allselenium ligand dsis (X = Se) yields the CuIII or NiIII chelate at once whereas with dmit using identical conditions the metal(II) compounds are formed.
    Notes: Ausgehend von Selenkohlenstoff und Selenschwefelkohlenstoff wird die elektrochemische Darstellung heterocyclischer Dichalkogenolate C3X52- (X = Se: dsis; X = S/Se: C3SxSey2-), die als Dibenzoylverbindungen isoliert und charakterisiert werden, beschrieben. Aus den mit Alkalimethanolat erhaltenen Verseifungslösungen dieser Dibenzoylverbindungen sind Metall-bis- und -tris-Chelate der heterocyclischen 1, 2-Dichalkogenolate vom Typ Am[M(C3X5)n] (A = Bu4N+, Ph4As+; M = ZnII, PtII, PdII, NiIII, CuIII, AuIII, InIII; X = Se, S/Se; m = 1, 2, 3; n = 2, 3) unmittelbar zugänglich. Cyclovoltammetrisch und mittels EPR werden die Nickel(III)-Verbindungen Bu4N[Ni(C3X5)2] (X = Se, S/Se) charakterisiert und der analogen Schwefelverbindung Bu4N[Ni(dmit)2] (X = S) gegenübergestellt. Für die bei der Chelatisierung mit dsis (X = Se) beobachtete Metall(II)-Metall(III)-Oxydation bei Kupfer und Nickel werden Argumente erörtert.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 548 (1987), S. 133-140 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: EPR Studies on Oxovanadium(IV) Bis-Complexes of 1,2-Dithio LigandsEPR investigations on oxovanadium(IV) bis-complexes containing the ligands 1,3-dithiol-2-thione-4,5-dithiolate, dmit2-, 1,2-dithiol-3-thione-4,5-dithiolate, dmt2-, and 1,2-dithiooxalate are reported. The parameters of the spin-Hamiltonian are used to characterize the bonding properties, and are compared with those obtained for the corresponding VOS4 chelates containing four-membered chelate rings. According to this a successful characterization of VOS4 type mixed-ligand complexes should be possible.
    Notes: Über EPR-Untersuchungen an Oxovanadium(IV)-bis-Komplexen der Liganden 1,3-Dithiol-2-thion-4,5-dithiolat, dmit2-, 1,2-Dithiol-3-thion-4,5-dithiolat, dmt2-, und 1,2-Dithiooxalat wird berichtet. Die erhaltenen Parameter des Spin-HAMILTON-Operators werden zur Charakterisierung der Bindungsverhältnisse benutzt und mit den für relevante VOS4-Vierringchelate erhaltenen verglichen. Der Parametervergleich eröffnet Möglichkeiten zur erfolgreichen Charakterisierung von Gemischtliganden-Komplexen, die eine VOS4-Koordinationssphäre enthalten.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 566 (1988), S. 131-136 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of 1,8-Dihydroxy-3,6-dithiaoctan-bis-mercury(II) ChlorideThe crystal structure of 1,8-dihydroxy-3,6-dithiaoctane-bis-mercury(II) chloride has been determined by X-ray crystal structure analysis. The compound crystallizes monoclinic, space group C2/c with a = 15.311(2), b = 5.870(2), c = 17.479(2) Å, β = 102.76° and 4 formula units per unit cell. The structure was solved by heavy atom technique and refined to a final R value of R = 0.050. Mercury is digonally coordinated by an S and a Cl ligator. In consequence of weak interactions to an oxygen atom of the ligand as well as to three further Cl ions the coordination number is increased to six and a strongly distorted octahedron is formed. The crystal structure is built up from polymeric complex molecules.
    Notes: Die Kristallstruktur von 1,8-Dihydroxy-3,6-dithiaoctan-bis-quecksilber(II)-chlorid wurde mittels Röntgenkristallstrukturanalyse bestimmt. Die Verbindung kristallisiert monoklin in der Raumgruppe C2/c mit a = 15,311(2), b = 5,870(2), c = 17,479(2) Å, β = 102,76°; Z = 4. Die Struktur wurde mit Hilfe der Schweratommethode gelöst und bis zu einem R-Wert von 0,050 verfeinert. Quecksilber wird von einem S- und einem Cl-Ligator digonal koordiniert. Infolge schwacher Wechselwirkungen zu einem Sauerstoffatom des Liganden sowie zu 3 weiteren Cl-Ionen erhöht sich die Koordinationszahl unter Ausbildung eines stark verzerrten Oktaeders auf 6. Die Kristallstruktur ist aus polymeren Komplexmolekülen aufgebaut.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of a Novel Dimetallamacrocycle: cyclo-Di[mercury-μ-[1,1,1′,1′-tetraethyl-3,3′-terephthaloyl-bis-thioureato(2-)-S:S′]]The structure of the title compound has been determined by an X-ray structure analysis. The compound crystallizes in the monoclinic space group P21/n with a = 13.437, b = 9.270, c = 18.791 Å, β = 100.65° and Z = 2. The solution of the structure was performed by Patterson methods. The final R value was R = 0.090 for 3089 observed reflections. The molecule has a cyclic structure consisting of two molecules of the ligand which coordinate only by the sulphur atoms and two mercury atoms. The formed ring is a 26-membered dimetallamacrocycle. The intramolecular Hg-Hg distance is 10.39 Å. The molecule has the symmetry Ci.
    Notes: Die Struktur der Titelverbindung wurde durch Röntgenkristallstruktur-analyse bestimmt. Die Verbindung kristallisiert monoklin in der Raumgruppe P21/n mit den Gitterkonstanten a = 13,437, b = 9,270, c = 18,791 Å, β = 100,65° und Z = 2. Gelöst wurde die Struktur mittels Patterson-Methoden. Der abschließende R-Wert betrug R = 0,090 für 3089 beobachtete Reflexe. Das Molekül besitzt eine zyklische Struktur, die sich aus zwei Molekülen des nur über die Schwefel-Atome koordinierenden Liganden und zwei Quecksilber-Atomen zusammensetzt. Der gebildete Ring ist ein 26gliedriger Dimetallamacrocyclus. Der intramolekulare Hg-Hg-Abstand beträgt 10,39 Å. Das Molekül besitzt die Symmetrie Ci.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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