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  • 1
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polysulfonyl Amines. XX. (1/1) Molecular Adducts of Di(organosulfonyl) Amines with Triphenylphosphine Oxide. X-Ray Structure Determination of Dimesylamine-Triphenylphosphine Oxide (1/1)From equimolar solutions of the respective components in organic solvents, crystalline addition compounds of composition (RSO2)2NH · OP(C6H5)3 are obtained, where R = CH3, C6H5, 4-X—C6H4 (X = CH3, F, Cl, Br, NO2) or 3-NO2—C6H4. (CH3SO2)2NH · OP(C6H5)3 crystallizes in the monoclinic space group P21/n. A short NH⃛O hydrogen bond [N⃛O 266.1(5) pm] connects the dimesylamine molecule with the triphenylphosphine oxide molecule.
    Notes: Aus äquimolaren Lösungen der jeweiligen Komponenten in organischen Lösemitteln werden kristalline Addukte der Zusammensetzung (RSO2)2NH · OP(C6H5)3 mit R = CH3, C6H5, 4-X—C6H4 (X = CH3, F, Cl, Br, NO2) sowie 3-NO2—C6H4 erhalten. (CH3SO2)2NH · OP(C6H5)3 kristallisiert in der monoklinen Raumgruppe P21/n. Eine kurze Wasserstoffbrücke des Typs NH⃛O [N⃛O 266,1(5) pm] verknüpft das Dimesylamin- mit dem Triphenylphosphinoxid-Molekül.
    Additional Material: 2 Ill.
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  • 2
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactivity of Phosphorus Pentahalides with Transition Metal Carbonyls. IV. Reactivity of Phosphorus Pentahalides with [CpM(CO)3]2 (M = Cr, Mo, W). Crystal Structure of CpCrCl2CH3CNPX5 (X = Cl, Br) reacts with cyclopentadienyl complexes of the type [CpM(CO)3]2 (M = Cr, Mo, W) at room temperature in high yields to give complexes CpCrX2CH3CN and CpMX4CH3CN (X = Cl, Br; M = Mo, W), respectively. The complexes were characterized by IR and ESR spectroscopy and magnetic measurements. CpCrCl2CH3CN crystallizes in the space group P21/c as a monomer with distorted tetrahedral geometry at chromium. The Cp ring is disordered.
    Notes: Die Reaktion von PX5 mit Cyclopentadienylderivaten des Typs [CpM(CO)3]2 (M = Cr, Mo, W; Cp = η5-C5H5) führt bei Raumtemperatur in hohen Ausbeuten zu den Halogeno-Komplexen CpCrX2CH3CN bzw. CpMX4CH3CN (X = Cl, Br; M = Mo, W). Die erhaltenen Derivate werden anhand der IR- und ESR-Spektroskopie, sowie der Messung magnetischer Daten charakterisiert. CpCrCl2CH3CN kristallisiert in der Raumgruppe P21/c als Monomer mit verzerrter tetraedrischer Geometrie am Chrom. Der Cp-Ring ist ungeordnet.
    Additional Material: 1 Ill.
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  • 3
    ISSN: 0044-2313
    Keywords: Diphenoxyphosphorylchloride ; N′,N′-dialkyl-N-diphenoxyphosphoryl urea ; N-diphenoxyphosphoryl-N″,N″-dipropyl biuret ; X-ray crystal structure analysis ; n.m.r. spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Diphenoxyphosphorylchloride with N,N-disubstituted Ureas - Formation of Phosphorylated Biuret CompoundsN′,N′-disubstituted N-diphenoxyphosphorylureas, (PhO)2P(O)—NH—CO—NR1R2 (R1 = R2 = Et, 1; n-Pr, 2; n-Bu, 3; i-Bu, 4; R1 = Me and R2 = Ph, 5) as well as phosphorylated biuret compounds, (PhO)2P(O)—NH—CO—NH—CO—NR1R2 are obtained in the reaction of diphenoxyphosphorylchloride with N,N-disubstituted ureas and triethylamine. The biuret derivatives are formed via (PhO)2P(O)NCO. Their yield rises if the reaction is carried out without amine. The X-ray crystal structure analysis of (PhO)2P(O)—NH—CO—NH—CO—NPr2, 8, shows that dimers exist in the crystal with intermolecular as well as intramolecular hydrogen bonds. The framework formed by atoms P—N1—C1(O4)—N2—C2(O5)—N3(C3)C6 is planar. The existence of a rotation barrier along the bond C2-N3 was detected by NMR spectroscopy.
    Notes: Bei der Umsetzung von Diphenoxyphosphorylchlorid mit N,N-disubstituierten Harnstoffen in Gegenwart von Triethylamin treten neben N′,N′-disubstituierten N-Diphenoxyphosphorylharnstoffen, (PhO)2P(O)—NH—CO—NR1R2 (R1 = R2 = Et, 1; n-Pr, 2; n-Bu, 3; i-Bu, 4; R1 = Me u. R2 = Ph, 5), immer auch N″,N″-disubstituierte N-Diphenoxyphosphorylbiuret-Verbindungen, (PhO)2P(O)—NH—CO—NH—CO—NR1R2 auf. Sie entstehen über intermediär gebildetes (PhO)2P(O)NCO. Die Ausbeute an Biuretderivaten steigt, wenn ohne Aminzusatz gearbeitet wird. Die Röntgen-Kristallstrukturanalyse von (PhO)2P(O)—NH—CO—NH—CO—NPr2, 8, zeigt, daß im Kristall Dimere mit sowohl inter- als auch intramolekularen Wasserstoffbrücken vorliegen. Das Gerüst von 8 mit der Atomfolge P—N1—C1(O4)—N2—C2(O5)—N3(C3)C6 ist nahezu planar. NMR-Untersuchungen beweisen die Existenz einer Rotationsbarriere um die Bindung C2-N3.
    Additional Material: 1 Ill.
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  • 4
    ISSN: 0044-2313
    Keywords: Mono- and di-t-butyclyclopentadienyl complexes of iron and molybdenum carbonyls ; binuclear complexes ; thermolysis ; X-ray structure analysis (Mo ; Mo) single and triple bond ; bis{dicarbonyl[n5-1, 3-di(t-butyl)cyclopentadienyl]molybdenum} (Mo≡Mo) ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mono- and Di-t-Butylcyclopentadienyl Carbonyl Complexes of Iron and Molybdenum  -  Crystal Structure of [Cp″Mo(CO)2]2 (Cp″ = n5-C5H3-t-Bu2-1,3)Cothermolysis of M(CO)m (M = Fe, m = 5; M = Mo, m = 6) with t-Bu-substituted cyclopentadienyls constitutes a simple synthesis of complexes of the type [Cp*M(CO)n]2 (CP* = n5-C5H3 (t-Bu), R, R = H, t-Bu; M = Fe, Mo; n = 2, 3). Each synthesis has an optimal temperature. The yield of Fe complexes decreases at temperatures above 130°C because of decomposition of the product. Optimal yields of [Cp*Mo(CO)3]2 are obtained at 130-140°C, whereas at 160°C complexes of the type [Cp*Mo(CO)2]2 with formal Mo—Mo triple bonds are obtained. The structure of the complexes is discussed on the basis of 1H-, 13C-NMR, IR, and mass spectrometry. The structure of [Cp″Mo(CO)2]2 (Cp″ = n5-C5H3t-Bu2-1,3) was determined by X-ray crystallography at -95°C. It crystallises in the space group Pbca, with cell constants a = 1808.6(6), b = 1308.5(4), c = 2507.9(9) pm, Z = 8, R = 0.031 for 3794 reflections. The Mo—Mo bond length of 253.3 pm is very long for a formal triple bond. The Cp″—Mo—Mo—Cp″ axis is non-linear.
    Notes: Die Cothermolyse der Metallcarbonyle M(CO)m (M = Fe, m = 5; M = Mo, m = 6) mit durch t-Butylgruppen mono- und disubstituierten Cyclopentadienen ist eine günstige Möglichkeit zur Darstellung von Komplexen des Typs [Cp*M(CO)n]2 (Cp* = n5-C5H3(t-Bu)R, R = H, t-Bu; M = Fe, Mo; n = 2, 3). Für die einzelnen Komplexe gibt es optimale Synthesetemperaturen. Wird bei der Darstellung der Fe-Derivate eine Temperatur von 130°C überschritten, sinkt die Ausbeute infolge von Zersetzungsreaktionen. Die Synthese der Komplexe [Cp*Mo(CO)3]2 erfolgt bei einer Temperatur von 130-140°C, während bei 160°C die Derivate [Cp*Mo(CO)2]2 mit formaler (MoMo)-Dreifachbindung erhalten werden. Die Strukturen der gebildeten Komplexe werden an Hand von 1H-, 13C-NMR-, IR- und Massenspektren diskutiert. Für [Cp″Mo(CO)2]2 (Cp″ = n5-C5H3t-Bu2-1,3) wurde bei-95°C eine Röntgenstrukturanalyse durchgeführt. Es kristallisiert in der Raumgruppe Pbca, mit den Gitterkonstanten a = 1808,6(6), b = 1308,5(4), c = 2507,9(9) pm. Z = 8, R = 0,031 für 3794 Reflexe. Der Mo—Mo-Bindungsabstand (253,3 pm) ist für eine formale Dreifachbindung sehr lang. Die Cp″—Mo—Mo—Cp″-Achse ist nicht linear.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1693-1698 
    ISSN: 0044-2313
    Keywords: Tris(trimethylsilyl)methaneselenenyl halides ; Tris(trimethylsilyl)methaneselenyl chalcogenides ; 1H, 13C, 77Se n.m.r. sprectra ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Tris(trimethylsilyl)methaneselenenyl Halides and Chalcogenides.Ditrisyldiselenide (1) (trisyl = TSi = (Me3Si)3C) reacts with SOCl2, Br2 and I2 to provide trisylselenenyl halides TSiSeX (2: X = Cl; 3: X = Br, 4: X = I). Insertion of S and Se into the Se—Se bond of 1 to yield (TSiSe)2Sn (5: n = 1; 6: n = 2) and (TSiSe)2Sen (7: n = 1; 8: n = 2) was catalysed by iodine. 5 was isolated in pure state and examined by X-ray diffraction. Triselenide 7 can be cleaved by I2 in CS2 to give 4 and Se2I2 (9). From 2 with Me3SiCN and Me3SiNCS, the new selenenyl pseudohalides TSiSeCN (10) and TSiSeSCN (11) were prepared. The compounds were characterised by 1H, 13C- and 77Se n.m.r. spectra.
    Notes: Ditrisyldiselenid (1) (Trisyl  -  Tsi  -  (Me3Si)3C—) reagiert mit SOCl2, Br2 und I2 zu Trisylselenenylhalogeniden TSiSeX (2: X = Cl; 3: X = Br, 4: X = I). Die Einschiebung von Schwefel und Selen in die Se—Se-Bindung von 1 zu (TSiSe)2 Sn (5: n = 1; 6: n = 2) bzw. (TSiSe)2Sen (7: n = 1; 8: n = 2) läßt sich mit Iod katalysieren. 5 wurde in reiner Form isoliert und durch Röntgenstrukturanalyse untersucht. Das Triselenid 7 wird durch Iod in CS2 zu 4 und Se2I2 (9) gespalten. Aus 2 lassen sich mit Me3SiCN bzw. Me3SiNCS das Trisylselenocyanat TSiSeCN (10) bzw. Trisylselenenylthiocyanat TSiSeSCN (11) gewinnen. 1H, 13C- und 77Se-NMR Spektren von 1 - 11 sind im Einklang mit den Strukturvorschlägen.
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1811-1811 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of (η2-Ethene)bis(triphenylphosphane)platinum(0) with Dimeric Hexafluorothioacetone. Preparation and Structure of Platina Cyclopentane and Cyclopropane DerivativesThe five-membered (CS)2Pt ring 1 was obtained by the reaction of 2, 2, 4, 4-tetrakis(trifluoromethyl)-1,3-dithietane and (η2-ethene)bis(triphenylphosphane)platinum(0) at low temperatures. 1 is converted at its melting point to the three-membered CSPt ring derivative 2, with elimination of one molecule of hexafluorothioacetone. 2 is also formed directly when the reaction is conducted at temperatures above +30°C. 2 was characterized by an X-ray Structural analysis.
    Notes: Der fünfgliedrige (CS)2Pt-Cyclus 1 kann aus 2, 2, 4, 4-Tetrakis(trifluormethyl)-1,3-dithietan und (η2-Ethen)bis(triphenylphosphan)-platin(0) bei tiefer Temperatur erhalten werden. 1 wandelt sich an seinem Schmelzpunkt unter Abspaltung eines Moleküls Hexafluorthioaceton in den um zwei Ringglieder reduzierten CSPt-Ring 2 um, der auch auf direktem Wege durch Umsetzen des Dithietans bei Temperaturen oberhalb von +30° zugänglich ist. 2 konnte erstmals durch eine Kristallstrukturbestimmung charakterisiert werden.
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 601 (1991), S. 111-119 
    ISSN: 0044-2313
    Keywords: Sulfonyl amines ; bis(dimesylamino)dimethyl silane ; bis(dimesylamino)dimethyl stannane ; preparation ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polysulfonyl Amines. XXIV. Preparation and Crystal Structures of Bis(dimesylamino)dimethyl Silane and Bis(dimesylamino)dimethyl StannaneThe new compounds (CH3)2E[N(SO2CH3)2]2 with E = Si (3), m.p. 162 °C, and E = Sn (4), m.p. 194-196 ° were prepared by metathesis of AgN(SO2CH3)2 with (CH3)2ECl2 and subjected to X-ray structure determinations. 3 crystallizes in the monoclinic space group C2/c with a = 1714.3(4), b = 679.6(2), c = 1389.9(4) pm, β = 97.50(2)° and Z = 4, 4 in the same space group with a = 2093.8(8), b = 1320.7(6), c = 1443.9(6) pm, β = 124.28(3)° and Z = 8. The crystals of both compounds consist of discrete monomeric molecules, in which the central atom E is bonded to two carbon and two nitrogen atoms in an approximately tetrahedral geometry for 3 [angles at Si in the range (105.5⃛111.9)°] and in a severely distorted tetrahedral arrangement in 4 [CSnC 128.8°; NSnN 107.8°; NSnC in the range (99.9⃛109.4)°]. Details of the molecular structures suggest that in each molecule two intramolecular E⃛O dipole-dipole interactions are stereochemically significant [Si⃛O 291.4 pm (2x); Sn⃛O 300.9 and 303.1 pm]. The molecule of 3 displays an exact, that of 4 an approximate twofold symmetry.
    Notes: Die neuen Verbindungen (CH3)2E[N(SO2CH3)2]2 mit E = Si (3), Schmp. 162 °C, und E = Sn (4), Schmp. 194-196 °C, wurden durch Metathese von AgN(SO2CH3)2 mit (CH3)2ECl2 erhalten und röntgenstrukturanalytisch charakterisiert. 3 kristallisiert in der monoklinen Raumgruppe C2/c mit a = 1714,3(4), b = 679,6(2), c = 1389,9(4) pm, β = 97,50(2)° und Z = 4, 4 in der gleichen Raumgruppe mit a = 2093,8(8), b = 1320,7(6), c = 1443,9(6) pm, β = 124,28(3)° und Z = 8. Die Kristallpackung beider Verbindungen besteht aus diskreten monomeren Molekülen, in denen das Zentralatom E an zwei Kohlenstoff- und zwei Stickstoffatome gebunden ist. 3 weist eine annähernd tetraedrische Geometrie auf [Winkel am Siim Bereich (105,5⃛111,9)°], 4 hingegen eine stark verzerrte Tetraedergeometrie [CSnC 128,8°; NSnN 107,8°; NSnC im Bereich (99,9⃛109,4)°]. Eine Betrachtung der Molekülstrukturen legt nahe, daß in beiden Fällen je zwei intramolekulare (E⃛O)-Wechselwirkungen vom Dipol-Dipol-Typ die Stereochemie beeinflussen [Si⃛O 291,4 pm (2x) Sn⃛O 300,9 und 303,1 pm]. Das Molekül von 3 besitzt eine strenge, das von 4 eine annähernde zweizählige Symmetrie.
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