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  • Inorganic Chemistry  (5)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 428-435 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diazadienes as Controlling Ligands in Homogeneous Catalysis, IX Catalytic Cyclotetramerization of Propynoic EstersPropynoic esters HC≡C—CO2R 2 react at low temperature in cyclohexane in the presence of precatalysts of the type of diazadiene-nickel(0) complexes 3 and 4 or diazadiene-nickel-(η2-alkyne) complexes such as 5b to give exclusively or preponderantly cyclooctatetraene tetracarboxylic esters 7. From 1H and 13C NMR data and by chemical methods a 1,3,6,8-substitution pattern (symmetry C2) is established.
    Notes: Propiolsäureester HC≡C—CO2R 2 lassen sich bei niedriger Temperatur in Cyclohexan an Präkatalysatoren vom Typ der Diazadien-Nickel(0)-Komplexe 3 bzw. 4 oder an Diazadien-Nickel-(η2-Alkin)-Komplexen wie 5b vollständig oder überwiegend zu Cyclooctatetraen-tetracarbon-säureestern 7 umsetzen. Aus 1H- und 13C-NMR-Daten sowie mit chemischen Methoden ergibt sich ein 1,3,6,8-Substitutionsmuster (Symmetrie C2).
    Additional Material: 1 Tab.
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  • 2
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diazadienes as Controlling Ligands in Homogeneous Catalysis, VII1). Catalytic Synthesis and Structure of a Cyclooctatetraene with Twofold Vicinal Substitution - 1,4,5,8-Tetrakis[(p-tolyloxy)methyl]-1,3,5,7-cyclooctatetraeneThe catalytic reaction of 2-propynyl p-tolyl ether (propargyl p-tolyl either) with the diazadiene nickel complex 4 gives a highly symmetrical cycloocatetraene derivative 2. 1H NMR and 13C NMR spectra do not allow to distinguish between three possible substitution patterns (1,3,5,7; 1,4,5,8; 1,2,5,6). Double bond and substituent positions were determined by an X-ray structural analysis. The encountered pattern with a twofold vicinal substitution (1,4,5,8) was hitherto unknown for catalytically prepared cycloocatatetraenes. At the same time, 2 is the first cyclotetramer of a propargylic ether.
    Notes: Die katalytische Umsetzung von 2-Propinyl-p-tolylether (Propargyl-p-tolylether) mit dem Diazadien-nickelkomplex 4 führt zu einem hochsymmetrischen Cyclooctatetraenderivat 2. 1H-NMR- und 13C-NMR-Spektren erlauben aus Symmetriegründen keine Unterscheidung zwischen drei möglichen Substitutionsmusten (1,3,5,7; 1,4,5,8; 1,2,5,6). Durch eine Röntgenstrukturanalyse wurden die Substituentenstellung und die Lage der Doppelbindungen bestimmt. Das gefundene, doppelt vicinale 1,4,5,8-Substitutionsmuster war für katalytisch dargestellte Cyclooctatertraene bis jetzt unbekannt; zugleich ist 2 das erste Cyclotetramere eines Propargylethers.
    Additional Material: 2 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 518 (1984), S. 101-114 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ag6B10S18: A Novel Thioborate with Tetrahedral Coordination of BoronAg6B10S18 was prepared as a novel thioborate from the reaction of stoichiometric amounts of Ag2S, B, and S at 700°C with successive annealing at 580-460°C. The orange-yellow compound crystallizes in the monoclinic space group C2/c with a = 21.663(8), b = 21.639(8), c = 16.572(5) Å, ß = 129.40(4)°, Z = 8, dx = 2.948 g · cm-3. According to the complete X-ray crystal structure analysis the anionic part of the Ag6B10S18 structure contains B10S20 “supertetrahedra” consisting of ten parallel corner-sharing BS4 tetrahedra; the B10S20 groups are linked through corners to form a layer-like arrangement of (B10S16S4/26-)n = (B10S186-)n polyantions. The mean B—S bond length is 1.915 Å. The electron densities in the regions of the Ag+ ions show a dynamically disordered arrangement which can be described by a distribution of the 6 Ag+ ions of the asymmetric unit over 18 partially occupied sites, these structural characteristics making Ag6B10S18 an Ag+ ionic conductor. The i.r. spectrum of the compound shows B—S stretching vibrations at 610, 640, 685, 735, and 760 cm-1.
    Notes: Ag6B10S18 wurde als neues Thioborat aus Ag2S, Bor und Schwefel bei 700°C mit anschließendem Tempern bei 580-460°C dargestellt. Die orange-gelbe Verbindung kristallisiert monoklin, Raumgruppe C2/c, mit a = 21,663(8), b = 21,639(8), c = 16,572(5) Å, ß = 129,40(4)°, Z = 8, drönt. = 2,948 g · cm-3. Wie die vollständige Röntgenstrukturanalyse zeigt, enthält Ag6B10S18 im anionischen Teil B10S20-„Supertetraeder“, die aus zehn parallelen, über Ecken verknüpften BS4-Tetraedern bestehen; die B10S20-Gruppen sind über Ecken schichtartig zu (B10S16S4/26-)n = (B10S186-)n-Polyanionen verbunden. Die mittlere B—S-Bindungslänge beträgt 1,915 Å. Die Elektronendichte im Bereich der Ag+-Ionen zeigt eine dynamische fehlgeordnete Anordnung, die durch eine Verteilung der 6 Ag+-Ionen der asymmetrischen Einheit auf 18 partiell besetzte Punktlagen beschrieben werden kann. Damit sind die strukturellen Voraussetzungen für Ag+-Ionenleitung gegeben. Das IR-Spektrum zeigt B—S-Valenzschwingungen bei 610, 640, 685, 735 und 760 cm-1.
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1943-1950 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Bis(diazadine)iron(0) ComplexesReduction of iron(II) compounds with alkali metal or via an alkylation with Grignard reagents in the presence of 1,4-diaza-1,3-dienes (DAD) yields the brown, paramagnetic, tetracoordinate iron(O) complexes Fe(DAD)2 2. Depending on the bulkiness of the DAD substituents, carbon monoxide does not add or adds more or less readily and reversibly to give deep green diamagnetic (DAD)2Fe(CO) 6, or in an irreversible manner to give red (DAD)-Fe(CO)3 8. A corresponding colour change occurs during the addition reactions of 2 are observed with dicyanogen, nitrosyl chloride, or a diazoalkane. Two molecules of a dialkyl acetylenedicarboxylate are added to sterically not too demanding complexes 2 and with concomitant C—C bond formation an airstable, deeply blue coloured ferracyclopentadiene 9 is formed. A single crystal X-ray investigation of monoclinic 9b was performed. The molecules of symmetry C2 contain two DAD-chelates and a tetrakis(alkoxycarbonyl)-1,3-butadiene-1,4-diyl chelate at the octahedral iron(II) center.
    Notes: Bei der Reduktion von Eisen(II)-Verbindungen mit Alkalimetallen oder über eine Alkylierung mit Grignard-Reagenzien in Gegenwart von 1,4-Diaza-1,3-dienen (DAD) entstehen die paramagnetischen, braunen, vierfach koordinierten Eisen(O)-Komplexe Fe(DAD)2 2. Je nach Größe der DAD-Substituenten addieren sie nicht, langsam oder rasch reversibel Kohlenoxide zu den diamagnetischen, labilen, tiefgrünen (DAD)2Fe(CO) 6 bzw. irreversible zu den stabilen, roten (DAD)Fe(CO)3 8. Auch Isocyanide zeigen unter Addition zu analogen 7 und 10 entsprechende Farbreaktionen. Ebenso wird mit Dicyan, Nitrosylchlorid oder Diazoalkan Addition beobachtet. An sterisch nicht zu anspruchsvolle 2 werden zwei Moleküle Acetylendicarbonester unter C—C-Verknüpfung zu einem tiefblauen, luftstabilen Ferracyclopentadien 9 addiert. Eine Einkristall-Röntgenstrukturanalyse an monoklinem 9b wurde durchgeführt. Das C2-symmetrische Komplexmolekül enthält zwei DAD-Chelatliganden und einen chelatgebundenen Tetrakis(alkoxycarbonyl)-1,3-butadien-1,4-diyl-Liganden am oktaedrisch koordinierten Eisen(II)-Zentrum.
    Additional Material: 4 Ill.
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  • 5
    ISSN: 0009-2940
    Keywords: Tin complexes ; Transition metal complexes ; NMR, 119Sn ; Sn(0) compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two Extremes in Tin Chemistry: A Non-bonding Sn-Sn Distance of 285 pm and a 119Sn-NMR Shift δ = 3301 in Organome-tallic Derivatives of Sn(0)The reaction of Na[{Cp'(CO)2Mn}2H] with SnCl2, which produces the inidene compound [Cp'(CO)2Mn\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ {\rm C}\ddot - {\rm C} $\end{document}Sn(Cl)\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ {\rm C}\ddot - {\rm C} $\end{document}Mn-(CO)2Cp']- under standard workup procedures, results in the formation of [{Cp'(CO)2MnSn}2{μ2-Mn(CO)2Cp'}2{μ2-Cl}]- (1) when quenched with unpolar solvents. While, formally, 1 contains tin in its oxidation state zero, it may be conceived as composed of an Sn2-2 entity, which is linearly end-on coordinated to two Cp'(CO)2Mn 16-electron species; in addition the tin centers are bridged by two μ2-Mn(CO)2Cp' moieties and a μ2-Cl function. The resulting connectivity Sn2{μ2-Mn(CO)2Cp'}2{μ2-Cl} thus corresponds to a [1.1.1]propellane scaffolding. While there is no obvious need for a tin-tin bond in this propellane-type cage, a short Sn-Sn contact of only 285 pm is observed. While the 119Sn-NMR signal of 1 could not be recorded, the peculiar bonding in this type of compounds is generally mirrored in their unconventional 119Sn-NMR shift whereever signals can be observed: it is found that [{Cp*(CO)2Mn}3(μ3-Sn)], which contains trigonally planar-coordinated μ3-Sn as a naked ligand atom, has its 119Sn-NMR resonance at δ = 3301 well beyond the known range of 119Sn-NMR shifts. This finding is interpreted in terms of a relatively week Snpπ-Mndπ π bonding which leads to low-energy unoccupied molecular orbitals as the prerequisit for a large paramagnetic contribution to the NMR shift.
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