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  • Inorganic Chemistry  (17)
  • Active centers  (1)
  • Bicyclo[3.2.1]octanes, stereoselective syntheses of  (1)
  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 239-242 
    ISSN: 0009-2940
    Keywords: 1-Naphthalenecarbonitrile, photochemistry of ; Cyclobutanes ; Captodative substitution ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photoexcited 1-naphthalenecarbonitrile (1) adds 2-morpholinoacrylonitrile (2) in the [2 + 2] mode both at the C(1) - C(2) and C(7) - C(8) bond unidirectionally and with the formation of only one (3 and 4, respectively) of the two a priori possible stereoisomers in each case. The structure of 3 has been unambiguously confirmed by an X-ray structural analysis.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 12
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Salts of S4N4O2 - Examples for the Dependence of the Structure of Cyclic Sulfur-Nitrogen Compounds on the Electron DensityThe reaction of S4N4O2 with nucleophiles (alcoholates, alcohols, azides, and isocyanates) in alcoholic solution leads to the salts 1a-h. The Structure of 1h was determined by means of an X-ray analysis. 1h crystallizes in the space group P21/n and contains a transannular S—S-bond with 248.2 (2) pm. The structure of 1h is considered in connection with the increase of electron density and compared with the results of the X-ray analysis of CH3Si(NSN)3SiCH3 (2). 2 is cubic (space group P4132). The bicyclic molecule (S—N 150.4(2), Si—N 173.7 (2) pm) has approximate D3h symmetry and shows no S—S bonds across the rings.
    Notes: Die Umsetzung von S4N4O2 mit Nucleophilen (Alkoholate, Alkohole, Azide und Isocyanate) in alkoholischem Medium führt zu den Salzen 1a-h. Für 1h wurde eine Röntgenstrukturanalyse durchgeführt. 1h kristallisiert in der Raumgruppe P21/n und enthält eine transannulare S—S Bindung mit 248.2 (2) pm. Die Struktur von 1h wird im Zusammenhang mit der Zunahme der Elektronendichte betrachtet und mit den Ergebnissen der Röntgenstrukturanalyse von CH3Si(NSN)3SiCH3 (2) verglichen. 2 kristallisiert kubisch (Raumgruppe P4132). Das bicyclische Molekül (S—N 150.4 (2), Si—N 173.7 (2)pm) hat praktisch D3h Symmetrie und zeigt keine S—S-Bindungen im Ring.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 1448-1459 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Substitution Reactions at Tetrasulfur TetranitridedichlorideThe reaction of S4N4Cl2 (1) with trimethylsilyl-substituted sulfodiimides in the molar ratio 1:1 leads to derivatives of pentasulfur hexanitride 2a and b. The structure of 2a was established by single X-ray crystal analysis. 1 reacts with trimethylsilyl-substituted amines to yield 1,5-bis(amino)-tetrasulfur tetranitrides 3a-c. The different orientation of the substituents was established by temperature-dependent 1H NMR investigations. In 2 and 3 the cage structure of the unsubstituted S4N4 is preserved.
    Notes: Durch Reaktion von S4N4Cl2 (1) mit trimethylsilyl-substituierten Sulfodiimiden im Molverhältnis 1:1 erhielten wir Derivate des Pentaschwefelhexanitrids 2a und b. Die Struktur von 2a wurde anhand einer Einkristallröntgenstrukturanalyse aufgeklärt. 1 reagiert mit trimethylsilyl-substituierten Aminen zu den 1,5-Bis(amino)tetraschwefeltetranitriden 3a-c. Die unterschiedliche Orientierung der Substituenten konnte durch temperaturabhängige 1H-NMR-Untersuchungen belegt werden. In 2 und 3 bleibt die Käfigstruktur des freien S4N4 erhalten.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1107-1117 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangement with Oxygen-Insertion in Azabicyclic Hydroxylamine DerivativesN-Hydroxy-2-azabicyclo[2.2.1]hept-5-ene (1) is rearranged to the oxaazabicyclic compounds 3, 4, and 8 by the reaction with either tosyl or benzoyl chloride. The structure of 3 was proved by X-ray analysis. Experiments with [18O]tosyl chloride as well as products of the intermediate 12 with methanol are consistent with a heterolysis in the intermediate 11 formed by N-tosylation  -  in contrast to the homolytic1) Meisenheimer rearrangement.
    Notes: N-Hydroxy-2-azabicyclo[2.2.1]hept-5-en (1) wird bei der Umsetzung mit Tosyl- und Benzoylchlorid umgelagert zu den Oxaazabicyclen 3, 4 und 8. Die Struktur von 3 wurde durch Röntgenstrukturanalyse bewiesen. Versuche mit [18O]Tosylchlorid sowie die Abfangprodukte mit Methanol sprechen für eine ionische Spaltung in dem durch N-Tosylierung gebildeten Intermediären 11, im Gegensatz zum radikalischen Ablauf der sonst analogen Meisenheimer-Umlagerung.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 15
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Existence of a Silaolefin: Synthesis and Crystal Structures of Wittig and Diels-Alder Products in Reactions of Lithiated (Fluorosilyl)diazasilacyclopentenes with Benzaldehyde and MethacroleinLithium salts of 1,2-diaza-3-sila-5-cyclopentenes react with fluorosilanes and aminofluorosilanes to give 4-(fluorosilyl)-substituted compounds 1 - 4. By reaction with tert-butyllithium 1 - 4 themselves form lithium salts 5 - 8, which react with fluorosilanes in a second substitution giving 9 and 10.5 and 7 undergo a Wittig-type reaction with benzaldehyde to form the benzylidene derivative 11. Spirocyclic Diels-Alder adducts (12, 13) are obtained from the reaction of 5 and 6 with 2-methyl-2-propenal. The propenylidene derivative 14 is formed as a by product. With excess 2-methyl-2-propenal, 12 reacts as a dienophile giving the oligocyclic Diels-Alder adducts 15 and 16. The crystal structures of 11 and 15 are reported.
    Notes: Lithiumsalze der 1,2-Diaza-3-sila-5-cyclopentene reagieren mit Fluorsilanen und Aminofluorsilanen zu den 4-(Fluorsilyl)-substituierten Verbindungen 1 - 4. In Reaktion mit tert-Butyllithium bilden 1 - 4 erneut Lithiumsalze (5 - 8), die mit Fluorsilanen unter Zweitsubstitution zu 9 und 10 reagieren. In Wittig-analoger Reaktion reagieren 5 und 7 mit Benzaldehyd zum Benzyliden-Derivat 11. Spirocyclische Diels-Alder-Addukte (12, 13) werden aus 5 und 6 mit 2-Methyl-2-propenal erhalten. Als Nebenprodukt entsteht das Propenyliden-Derivat 14. Mit überschüssigem Dien (2-Methyl-2-propenal) reagiert 12 als Dienophil zu den oligocyclischen Diels-Alder-Addukten 15 und 16. Kristallstrukturen von 11 und 15 werden mitgeteilt.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 16
    ISSN: 0009-2940
    Keywords: 1,2-Dihydro-1,3,2λ5,4λ5-diazadiphosphete ; Isomerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2-Dihydro-1,3,2λ5,4λ5-diazadiphosphete - Synthesis, Structure and Isomerization to the „Inner Salt“ of 1,3,2,4λ5-Diazadiphosphetan-2-ium HydroxideThe photochemical reaction of the azidophosphane (iPr2N)2PN3 (1) with the tetraazaphospholene (3) and the bis(imino)phosphorane (Me3Si)2NP(=NSiMe3)2 (6) proceeds by elimination of N2 to yield (5) and by 1,3-silyl group shift to furnish (8) the structures of which were determined by means of NMR data and, in the case of 5, additionally by X-ray structure analysis.
    Additional Material: 1 Ill.
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  • 17
    ISSN: 0044-2313
    Keywords: Potassium dithiocarbiminate ; dithiolates ; X-ray structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure of [ImNCS2K] (ImN = 1,3-Dimethylimidazoline-2-imino): a Novel Potassium DithiocarbiminateThe reaction of the 2-iminoimidazoline 4 with KMe gives the potassium imidate 7 from which the potassium 1,1-dithiolate 8 is obtained in almost quantitative yield. Crystals of C6H8N3S2K · 1/6 CH3CN (8 · 1/6 CH3CN) are triclinic, space group P1, Z = 6, a = 10.988(4), b = 13.597(8), c = 13.622(9) Å, α = 113.003, β = 105.53(3), γ = 105.62(3)°, V = 1636.90 Å3. The structure consists of a complicated 3-dimensional framework in which the K2 units bridged by the four sulfur atoms of two thiolate ligands are connected by nitrogen and sulfur bridges.
    Notes: Die Umsetzung des 2-Iminoimidazolins 4 mit KMe ergibt das Kaliumimidat 7, aus dem das Kalium-1,1-dithiolat 8 in fast quantitativer Ausbeute erhältlich ist. C6H8N3S2K · 1/6 CH3CN (8 · 1/6 CH3CN) kristallisiert triklin, Raumgruppe P1, Z = 6, a = 10.988(4), b = 13.597(8), c = 13.622(9) Å, α = 113.00(3), β = 105.53(3), γ = 105.62(3)°, V = 1636.90 Å3. Die komplexe Raumnetzstruktur besteht aus den durch die 4 Schwefelatome zweier Dithiolat-Liganden verbrückten K2-Einheiten, die ihrerseits über Stickstoff- und Schwefelatome verbunden sind.
    Additional Material: 2 Ill.
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  • 18
    ISSN: 0570-0833
    Keywords: Thiols ; Bioinorganic chemistry ; Active centers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thiolates are presently a subject of great interest in the chemistry of complexes involving transition-metal elements and soft ligands. The manifold electronic and steric capabilities offered by the monodentate ligands RS⊖ and the bidentate chelate ligands ⊖SRS⊖ have been used to stabilize a broad spectrum of mononuclear, oligomeric, and polymeric complexes with new and remarkable structures and properties. Impetus has especially been provided by the synthesis of polynuclear cagelike homo- and heteroleptic metal-sulfur frameworks, which can often be regarded as “molecular fragments” of the structures of inorganic sulfides. Thiolates and mixed sulfide-thiolates of the late open- and closed-shell 3d metals (Fe, Co, Ni, Cu, Zn) and some of their homologues (Au, Cd, Hg), as well as of Mo, are of particular importance as model complexes for biologically important metal centers coordinated by sulfur. They have played an important role in increasing our understanding of the structure, bonding, and function of the reactive centers in ferredoxins, rubredoxins, nitrogenases, blue copper proteins, metallothioneins, and antiarthritic drugs.
    Additional Material: 41 Ill.
    Type of Medium: Electronic Resource
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