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  • 1
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 2117-2122 
    ISSN: 0009-2940
    Schlagwort(e): 1λ4,3λ4,5λ4-Trithiatriazines ; Anomeric effect ; Antiaromaticity ; Calculations, ab initio, MNDO ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 2123-2127 
    ISSN: 0009-2940
    Schlagwort(e): 1λ4,3λ4-Dithiatriazines ; Calculations, MNDO ; Anomeric effect ; Electron diffraction ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 39-45 
    ISSN: 0009-2940
    Schlagwort(e): 1,3,2,4,6-Dithiatriazines ; CNS Polycycles, structure determination ; Calculations, MNDO ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1347-1352 
    ISSN: 0009-2940
    Schlagwort(e): 1α4,2,4,6-Thiatriazines, preparation, structures ; 1α4,2,4,6-Thiatriazinium cations ; Calculations, MNDO ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 2411-2416 
    ISSN: 0009-2940
    Schlagwort(e): Sulfur imides, N-(fluoroformyl)-, preparation of, reactions with AsF5 ; Isocyanatosulfonium salts, preparation and structures of ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 535-539 
    ISSN: 0009-2940
    Schlagwort(e): Dithietanes, fluoro- and fluorooxo-; formation of, cleavage with halogen fluorides, gas phase structure ; Lewis acids, containing fluorine ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 29-34 
    ISSN: 0009-2940
    Schlagwort(e): 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
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1353-1356 
    ISSN: 0009-2940
    Schlagwort(e): Difluoromethane, bis(trifluoro-α4-sulfanyl), bis(halosulfinyl) ; Bis(sulfinamides) ; 1α4,3α4,2-Dithiazetidines ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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).
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 2437-2439 
    ISSN: 0009-2940
    Schlagwort(e): Sulfur tetrafluoride imides ; Fluorosulfonylamines ; Pentafluorosulfanylamines ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reactions of (Fluorosulfonylimino)-λ6-sulfur Tetrafluoride FSO2N=SF4Herrn Professor Pedro J. Aymonino zum 60. Geburtstag gewidmet.FSO2N=SF4 (1) reacts with CsF, HF and CIF to form Cs+N(SO2F)SF5- (2), HN(SO2F)SF5 (3) and ClN(SO2F)(SF5) (5); 5 adds to ethylene to give ClCH2CH2N(SO2F)SF5 (6).
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 2601-2607 
    ISSN: 0009-2940
    Schlagwort(e): Thiatriazines, trichloro, preparation, structures ; Calculations, MNDO ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ChlorothiatriazinesFrom (ClSN)3 (1) and ClCN (2) 1,3,5-trichloro-1,3,2,4,6-dithiatriazine (ClCN)(ClSN)2 (3) was prepared in 26% yield. 3 reacts slowly further with excess 2 to give thiatriazine (ClCN)2(ClSN) (14) and triazine (ClCN)3 (16). A mechanism for the (ClSN)/(ClCN) exchange is proposed. The structures of 3, 14, and 16 have been determined by X-ray diffraction. The bonding situation in the system (ClSN)n(ClCN)3-n (n = 0 - 3) is discussed.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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