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  • 1
    Electronic Resource
    Electronic Resource
    Zur Existenz eines Silaolefins: Synthese und Kristallstrukturen von Wittig- und Diels-Alder-Produkten in Reaktionen lithiierter fluorsilylfunktioneller Diazasilacyclopentene mit Benzaldehyd und Methacrolein (1983)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 282-289 
    Details
    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
    URL: http://dx.doi.org/10.1002/cber.19831160132
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  • 2
    Electronic Resource
    Electronic Resource
    Umlagerung von azabicyclischen Hydroxylamin-Derivaten unter Sauerstoff-Insertion (1983)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1107-1117 
    Details
    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
    URL: http://dx.doi.org/10.1002/cber.19831160325
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  • 3
    Electronic Resource
    Electronic Resource
    Carbonylierende Ringerweiterung, 4. Diastereoselektive Synthesen von Bicyclo[3.2.1]oct-3-en-2,8-dionen durch doppelte Carbonylierung von (R)-(-)-α-Phellandren (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 1079-1087 
    Details
    ISSN: 0009-2940
    Keywords: Ring enlargement ; Phellandrene ; Carbonylation ; Bicyclo[3.2.1]octanes, stereoselective syntheses of ; Iron complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbonylating Ring Enlargement, 41). - Diastereoselective Syntheses of Bicyclo[3.2.l]oct-3-ene-2,8-diones by Double Carbonylation of (It)-(-)-α-PhellandreneIn order to clarify the stereochemistry of the carbonylating ring enlargement of cyclohexadiene complexes 1 to complexed seven-membered ring ketones 2 and the further carbonylation to bicyclo[3.2.1]oct-3-ene-2,8-diones 3 the exo and endo isomers of (R)-(-)-α-phellandrene complex 7 were synthesized in pure form and in various isomeric ratios and converted. The optically active ring-enlargement products 11 and 12 obtained therefrom, as well as the enantiomerically pure bicyclooctenes 20-22, implicate a stereospecific reaction course under retention of the configuration predetermined by the starting material 6 and its complexes 7. This was confirmed by an X-ray determination of the absolute configuration of exo-12. Thus, the method is suitable for the diastereoselective synthesis of bicyclo[3.2.1]oct-3-ene-2,8-diones 3 from 1,3-cyclohexadiene complexes 1.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901230522
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  • 4
    Electronic Resource
    Electronic Resource
    Derivate des Imidazols, IX. Stabilisierung von Selendiiodid durch KomplexbildungHerrn Professor Helmut Werner zum 60. Geburtstag gewidmet. (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 849-851 
    Details
    ISSN: 0009-2940
    Keywords: Selenium iodides ; Imidazoles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Imidazole Derivatives, IX.  -  Stabilisation of Selenium Diiodide by ComplexationHerrn Professor Helmut Werner zum 60. Geburtstag gewidmet.Stable selenium diiodide complexes 2 are obtained by the reaction of the 2-selenoxoimidazolines 1 with iodine. An X-ray structure analysis of 2c reveals its monomeric nature. In the trigonal bipyramid, the iodo substituents are situated in axial positions forming elongated iodine bonds [Se-I(1) 2.854(1), Se—I(2) 2.768(1) Å; I(1)—Se—I(2) 175.4(0)°].
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270511
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  • 5
    Electronic Resource
    Electronic Resource
    Kristall- und Molekülstrukturen des S3N2+-Radikalkations in S3N2+SO3CF3- · 1/2 CH3CN und von S3N2(NSO2F) (1980)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 226-232 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structures of the S3N2+ Radical Cation in S3N2+SO3CF3- · 1/2 CH3CN and of S3N2(NSO2F)The molecular and crystal structures of S3N2+SO3CF3- · 1/2 CH3CN (1) and S3N2NSO2F (2) were determined from single crystal X-ray diffraction data. The S3N2+ radical cation in 1 is planar, two cations being connected through weak S—S bonding interactions to form dimers with a chair configuration. The S3N2 ring of 2, in which the NSO2F group is covalently bonded to one of the S atoms of the S — S group, is not planar; the S — S bond is weaker than in 1.
    Notes: Die Röntgenstrukturanalysen von S3N2+SO3CF3- - 1/2 CH3CN (1) und S3N2NSO2F (2) zeigen in 1 ein planares S3N2+-Radikalkation, wobei zwei Kationen über schwache S-S-Wechselwirkungen zu sesselförmigen Dimeren assoziiert sind. Der an einem S-Atom der S — S-Gruppe substituierte S3N2-Ring in 2 ist nicht planar; die S — S-Bindung ist schwächer als in 1.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19801130123
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  • 6
    Electronic Resource
    Electronic Resource
    Substitutionsreaktionen an Tetraschwefeltetranitriddichlorid (1982)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 1448-1459 
    Details
    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
    URL: http://dx.doi.org/10.1002/cber.19821150423
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  • 7
    Electronic Resource
    Electronic Resource
    Einkernige Nickel-Thiolato-Komplexe mit Nickel-Zentren in unterschiedlichen Oxidationszuständen: Molekularer Aufbau von [Ni(SC6H4O)2]2- und [Ni(SC6H4O)2]Herrn Professor Dietrich Mootz zum 60. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 951-953 
    Details
    ISSN: 0009-2940
    Keywords: Thiolato ligands ; Nickel complexes ; Hydrogenase models ; Bioinorganic chemistry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mononuclear Nickel Thiolate Complexes Containing Nickel Sites in Different Oxidation States: Molecular Definition of [Ni(SC6H4O)2]2- and [Ni(SC6H4O)2]Herrn Professor Dietrich Mootz zum 60. Geburtstag gewidmet.A solution of NiCl2·6 H2O in EtOH/H2O reacts with nBu3N and o1-mercaptophenol to form [nBu3NH]2[Ni(SC6H4O)2]·EtOH (2) containing the nickel(II) complex [Ni(SC6H4O)2]2- (1). The molecular structures of 1 and its oxidation product, [Ni(SC6H4O)2]- (3), have been determined by X-ray diffraction. With respect to the chemical as well as electrochemical properties of the nickel sites of various hydrogenases, 3 is the first relevant model complex of coordination number four whose structural properties have been determined in different oxidation states.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260416
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  • 8
    Electronic Resource
    Electronic Resource
    Beiträge zur Chemie des Imidazols, III. 2-Telluroimidazoline  -  stabile Tellurocarbonyl-Verbindungen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 2047-2049 
    Details
    ISSN: 0009-2940
    Keywords: 2-Telluroimidazolines ; 125Te NMR ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Imidazole Chemistry, III[1].  -  2-Telluroimidazolines  -  Stable Tellurocarbonyl Compounds2-Telluroimidazolines 6 are obtained as stable solids from the imidazol-2-ylidenes 4 and tellurium in good yields. The X-ray structure of 6c reveals the relevance of the mesomeric structure 5 [d(C1 - Te) = 2.087(4) Å] which is confirmed by the upfield shift in the 125Te NMR spectra (dL 〈  - 150).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260914
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  • 9
    Electronic Resource
    Electronic Resource
    Compounds of Germanium and Tin, 22 - Reactions of a Silyene with a Germylene and a Stannylene: Formation of a Digermene with an Unusual Arrangement of the Substituents and of a Stannane (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1733-1737 
    Details
    ISSN: 0009-2940
    Keywords: Silicon ; Germanium ; Tin ; Carbene homologues ; Digermene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the diaminosilylene :Si(tBuNCH2CH2NtBu) (5) with the diaminogermylene :Ge(tBuNCH2CH2NtBu) is thought to proceed via a germasilene → silylgermylene rearrangement and dimerisation to furnish the (Z)-1,2-diamino-1,2-disilyldigermene (Z)-9. The X-ray structure analysis of (Z)-9 reveals a long Ge—Ge bond length of 245 pm and a large trans-bent angle of 42°. Air-oxidation of (Z)-9 takes place with retention of configuration at the germanium atoms to provide the corresponding substituted (Z)-2,4-digerma-1,3-dioxetane (Z)-10. Treatment of 5 with the stannylene :Sn[N(SiMe3)2)2 gives, as a final product, the hydridodisilylstannane 12. The structures of (Z)-10 and 12 were also determined by X-ray crystallography.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301205
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  • 10
    Electronic Resource
    Electronic Resource
    Light-Induced [2 + 2] Cycloaddition of 2-Morpholinoacrylonitrile to 1-Naphthalenecarbonitrile (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 239-242 
    Details
    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
    URL: http://dx.doi.org/10.1002/cber.19931260132
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