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  • 1
    Electronic Resource
    Electronic Resource
    Untersuchungen zur Lewis-Acidität fluorierter Sulfonium-IonenProfessor Alois Haas zum 60. Geburtstage gewidmet (1992)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 615 (1992), S. 117-122 
    Details
    ISSN: 0044-2313
    Keywords: Sulfonium salts ; Lewis acidity ; sulfuranonium salts ; persulfuranonium salts ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Lewis Acidity of Fluorinated Sulfonium IonsNMR investigations show, that sulfonium salts [(CF3)nSF3-n]+ AsF6- (1-3, n = 0-2) add CH3CN under formation of ψ-pentacoordinated sulfuranonium ions [(CF3)nSF3-n · NCCH3]+ (1a - 3a,) with the donor in an axial position. In solution NSF3 (4,) forms similar salts [(CF3)nSF3-n · NSF3]+ AsF6- (1b-3b,) with weaker donor-acceptor interactions. With NSF2NMe2 (5,) the step of the primary addition products is passed very quickly, by fluoride-migration from 1, and 2, persulfuranonium ions [(CH3)2NSF3NSF2]+ (6,) and [(CH3)2NSF3NSFCF3]+ (7,), respectively, are formed, while from 3, only decomposition products (Me2NSF2+, CF3SSCF3, CF4) were obtained.
    Notes: NMR-Untersuchungen zeigen, daß Sulfoniumsalze [(CF3)nSF3-n]+ AsF6- (1-3, n = 0-2) CH3CN addieren unter Bildung ψ-pentakoordinierter Sulfuranoniumionen [(CF3)nSF3-n · NCCH3]+ mit axialständigem Donor. NSF3 (4,) bildet in Lösung die analogen Salze [(CF3)n SF3-n · NSF3]+ AsF6- (1b-3b,) mit schwächerer Donor-Akzeptor-Wechselwirkung. Bei Umsetzungen mit NSF2NMe2 (5,), wird die Stufe der Primärprodukte sehr schnell durchlaufen; unter Fluoridwanderung kommt es mit 1, und 2, zur Bildung von Persulfuranonium-Ionen ([(CH3)2NSF3NSF2]+ (6,) bzw. [(CH3)2NSF3NSFCF3]+ (7,)), während aus der Umsetzung mit 3, nur Zersetzungsprodukte (Me2NSF2+, CF3SSCF3, CF4) erhalten wurden.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19926150924
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  • 2
    Electronic Resource
    Electronic Resource
    Reaktionen von Trihalogendithiatriazinen und Trifluortriazin mit Halogen-Lewis-Säuren (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1725-1728 
    Details
    ISSN: 0044-2313
    Keywords: Trihalodithiatriazines ; trihalotriazines ; salt-, adduct-formation ; X-ray structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Trihalodithiatriazines and Trifluorotriazine with Halogen-Lewis-Acids.From the reaction of (XCN)(XSN)2 and MX5 (X = Cl, M = Sb; X = F, M = As) the corresponding salts [(XCN)(XSN)(SN)]+MX6- (2, 4) are obtained. (FCN)3 adds AsF5 to the nitrogen-bonded adduct (FCN)3 · AsF5 (6). The X-ray-structure of 6 is reported.
    Notes: Aus der Umsetzung von (XCN)(XSN)2 und MX5 (X = Cl, M = Sb; X = F, M = As) werden die entsprechenden Salze [(XCN)(XSN)(SN)]+MX6- (2, 4) erhalten. (FCN)3 addiert AsF5 zu dem stickstoffgebundenen Addukt (FCN)3 · AsF5 (6). Die Röntgenstrukturanalyse von 6 wird mitgeteilt.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19936191017
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  • 3
    Electronic Resource
    Electronic Resource
    Zur Struktur von Trithiatriazinen (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 2117-2122 
    Details
    ISSN: 0009-2940
    Keywords: 1λ4,3λ4,5λ4-Trithiatriazines ; Anomeric effect ; Antiaromaticity ; Calculations, ab initio, MNDO ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Structure of TrithiatriazinesMNDO and ab initio calculations have shown that the structure of trithiatriazines [(RSN)3, where R = F, Cl, {H}] is influenced by the anomeric effect and by antiaromaticity of the ring for electron pairs in axial positions. These calculations are supported by a joint electron diffraction and microwave structure determination of (NSF)3 in the gas phase.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901231106
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  • 4
    Electronic Resource
    Electronic Resource
    Zum anomeren Effekt bei Dithiatriazinen (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 2123-2127 
    Details
    ISSN: 0009-2940
    Keywords: 1λ4,3λ4-Dithiatriazines ; Calculations, MNDO ; Anomeric effect ; Electron diffraction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Anomeric Effect in DithiatriazinesFrom (CF3CN3S2)n (1) and XeF2, Br2, or (CF3)2NO* the corresponding S,S-substituted dithiatriazines CF3CN3S2F2 (2), CF3CN3S2Br2 (3), and CF3CN3S2[ON(CF3)2]2 (4) are prepared. An electron diffraction study of 2 in the gas phase results in a slightly aplanar 6-membered ring with chair conformation and both S-F bonds in axial position. MNDO calculations show that the position of the substituents at the sulfur atoms is strongly dependent on these substituents and on the ring geometry. The cis preference is the result of an anomeric effect.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901231107
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  • 5
    Electronic Resource
    Electronic Resource
    Addition von Alkenen an 5-(Trifluormethyl)-1,3,2,4,6-dithiatriazin (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 39-45 
    Details
    ISSN: 0009-2940
    Keywords: 1,3,2,4,6-Dithiatriazines ; CNS Polycycles, structure determination ; Calculations, MNDO ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition of Alkenes to 5-(Trifluoromethyl)-1,3,2,4,6-dithiatriazinesDechlorination of 1,3-dichloro-5-(trifluoromethyl)-1,3,2,4,6-dithiatriazine (1) with Ph3Sb gives (CF3CN3S2)n (2) in quantitative yield. By 1,3-addition of alkenes (dicyclopentadiene, cyclopentene, cis- and trans-2-butene, propene, and ethene) to 2 the corresponding penta- (4a), tri-(5a), and bicyclic ring systems 6a, 6b, 7, 8a, 8b, and 9 are prepared in 65-85% yields. The molecular structures of 6a and 7 were determined by single-crystal X-ray analysis; the other structures were derived from NMR data. The NMR analyses are in accordance with MNDO calculations. For 4a and 5a only the thermodynamically favoured anti-isomers are found, as expected from these calculations; for 6 and 8 they show satisfactory agreement for anti/syn-proportions as determined by NMR spectroscopy. The product distribution corresponds to a symmetry-allowed alkene addition to a singlet dithiatriazine.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240107
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  • 6
    Electronic Resource
    Electronic Resource
    Synthese und Reaktionen von Bis(fluorsulfinyl)difluormethan, F2C(SOF)2 (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1353-1356 
    Details
    ISSN: 0009-2940
    Keywords: Difluoromethane, bis(trifluoro-α4-sulfanyl), bis(halosulfinyl) ; Bis(sulfinamides) ; 1α4,3α4,2-Dithiazetidines ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Reactions of Bis(fluorosulfinyl)difluoromethane, F2C(SOF)2From F2C(SF3)2 (1) and AsF5 the thermally labile monosulfonium salt F3SCF2SF2+ AsF6- (2) is prepared in SO2 as a solvent, while under the same conditions the corresponding tetrafluoroborate is solvolyzed to give an isomeric mixture of F2C(SOF)2 (5a,b). In the reaction of 5a,b with N-silylated amines F2C[S(O)NMe2]2 (7a,b), (8a,b), and (9a,b) are formed. The structure of the cis derivative 8b has been determined by X-ray diffraction. From 5a,b and HCl the rather unstable F2C[S(O)Cl]2 (10a,b) is obtained, which is hydrolyzed to F2C[S(O)OH]2 (11a,b).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240607
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  • 7
    Electronic Resource
    Electronic Resource
    Fluorthiatriazine (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1347-1352 
    Details
    ISSN: 0009-2940
    Keywords: 1α4,2,4,6-Thiatriazines, preparation, structures ; 1α4,2,4,6-Thiatriazinium cations ; Calculations, MNDO ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: FluorothiatriazinesFrom the reaction of (ClCN)2(ClSN) (1) with AgAsF6 in liquid SO2 (ClCN)2(SN)⊕ AsF⊖06 (2) is obtained in quantitative yield. With CsF 2 gives (ClCN)2(FSN) (3), which slowly dismutates at room temperature to form (ClCN)(FCN)(FSN) (4) and 1. Fluorination of 1 with SbF3 yields (FCN)2(FSN) (5). With AsF5 5 forms the salt (FCN)2(SN)⊕ AsF⊖ (6). The cation of 6 is transformed by NOCl or CsBr into the corresponding neutral derivatives (FCN)2(ClSN) (7) and (FCN)2(BrSN) (8), respectively. The gas-phase structure of 5 was determined by electron diffraction. The influence of the different exocyclic substituents on the bond properties in this ring system is explained by means of MNDO calculations.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240606
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  • 8
    Electronic Resource
    Electronic Resource
    Isocyanatosulfonium-Salze (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 2411-2416 
    Details
    ISSN: 0009-2940
    Keywords: Sulfur imides, N-(fluoroformyl)-, preparation of, reactions with AsF5 ; Isocyanatosulfonium salts, preparation and structures of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isocyanatosulfonium SaltsRR'SF2 reacts with Me3SiNCO to give the corresponding N-(fluoroformyl)sulfur imides FC(O)NSRR' [R = NMe2, R' = F (7); R' = CF3 (9)]. From these AsF5 abstracts F- with formation of isocyanatosulfonium salts ONC - SRR' + AsF-6 [R = F, R' = CF3 (6); R = NMe2, R' = F (8); R = NMe2, R' = CF3 (10)]. The spectroscopic properties of the fluoroformyl derivatives and of the isocyanato salts are discussed. The structures of 8 and 10 are determined by X-ray analyses.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911241106
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  • 9
    Electronic Resource
    Electronic Resource
    Fluor- und FluoroxodithietaneHerrn Professor Anton Meller zum 60. Geburtstag gewidmet. (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 535-539 
    Details
    ISSN: 0009-2940
    Keywords: Dithietanes, fluoro- and fluorooxo-; formation of, cleavage with halogen fluorides, gas phase structure ; Lewis acids, containing fluorine ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fluoro- and Fluorooxodithietanes (1) was isolated from the reaction of 2,2,4,4-tetrafluoro-1,3-dithietane (3) with CIF in an unpassivated monelcylinder. The hydrolysis of 1 gives (2): the trans derivative (2b) and the cis isomer (2a) are formed in a 4:1 ratio. (7) is oxidized by CIF at room temperature to give the known (8) in 87% yield. At 50°C from 8 and (9) is formed besides the ring cleavage products CF3SO2CF2SF4Cl (10) and CF3SO2CF2SF5 (11). The gasphase structure of 9 (e.d.) is described. (5) and (13) coordinate by the oxygen of the SO group to AsF5, with an unstable sulfonium salt is formed, while from the reaction of AsF5 and SbF5 with 8 (15 a, b, M = As, Sb) are isolated.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250302
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  • 10
    Electronic Resource
    Electronic Resource
    7-(Trifluormethyl)-1λ4,3λ4,5λ4,-trithia-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1(9),2,3,5,7-pentaen als Komplexligand (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 29-34 
    Details
    ISSN: 0009-2940
    Keywords: 1λ4,3λ4,5λ4,-Trithia-2,4,6,8,9-pentaazabicyclo [3.3.1]nona-1(9),2,3,5,7-pentaene, 7-trifluormethyl derivative, reactivity of / Coordination chemistry in liquid SO2 / Nickel(II) complexes with CF3CN5S3 / Sulfur dioxide, O-coordination to Ni(II) / Silver complexes with CF3 CN5S3 ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 7-(Trifluormethyl)-1λ4,3λ4,5λ4,-trithia-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1(9),2,3,5,7-pentaene as Ligand in Coordination ChemistryMany possibilities exist for the title compound CF3CN5S3 (3) (L) to coordinate to transition metal centers. From the reaction of 3 with [Ni(SO2)2](AsF6)2 and AgAsF6 in liquid SO2 [Ni-(SO2)2L2(FAsF5)2) (11) and [AgL]AsF6 (13) or [AgL2]AsF6 (14), respectively, were isolated. As shown by X-ray structure determination of 11 and 14, L coordinates as expected from MNDO calculations.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901230107
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