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  • IR Spectra  (5)
  • crystal structures  (5)
  • syntheses  (5)
  • Nitrido ligand  (2)
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  • 11
    ISSN: 0044-2313
    Keywords: Phosphorane Iminato Complexes of Sulfur ; Syntheses ; IR Spectra ; Crystal Structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Phosphorane Iminato Complexes of Sulfur. Synthesis and Crystal Structures of [SO(Cl)(NPPh3)], [SO2(Cl)(NPPh3)], and [SCl(NPPh3)2]ClThe title compounds have been prepared by the reaction of Me3SiNPPh3 with SOCl2, SO2Cl2, and SCl2, respectively. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations.[SO(Cl)(NPPh3)]: Space group P21/n, Z = 4, structure determination with 2 434 observed unique reflections, R = 0.047. Lattice dimensions at 19°C: a = 1 304.8, b = 996.5, c = 1 339.5 pm, β = 93.75°. The compound forms monomeric molecules with a remarkably long S—Cl bond of 234.2 pm and distances SN and PN of 154.6 and 161.6 pm, respectively, which agree with double bonds.[SO2(Cl)(NPPh3)]: Space group P21/n, Z = 4, structure solution with 2 872 observed, unique reflections, R = 0.047. Lattice dimensions at 20°C: a = 956.9, b = 1 909, c = 1 002.0 pm, β = 106.06°. The compound forms monomeric molecules with distances S—Cl of 207.1 pm, SN of 154.5 pm, and PN of 161.6 pm.[SCl(NPPh3)2]Cl: Space group P21/c, Z = 4, structure solution with 5 224 observed, unique reflections, R = 0.042. Lattice dimensions at 20°C: a = 1 108.6, b = 1 603.8, c = 1 840.5 pm, β = 99.98°. The compound forms ions [SCl(NPPh3)2]+ and Cl-. In the cation the sulfur atom is ϕ-tetrahedrally coordinated with a long S—Cl distance of 248.5 pm and SN bond lengths of 154.5 and 156.0 pm.
    Notes: Die Titelverbindungen entstehen durch Umsetzung von Me3SiNPPh3 mit Thionylchlorid, Sulfurylchlorid bzw. Schwefeldichlorid als farblose, feuchtigkeitsempfindliche Kristalle, die wir durch die IR-Spektren und durch Kristallstrukturanalysen charakterisiert haben.[SO(Cl)(NPPh3)]: Raumgruppe P21/n, Z = 4, Strukturlösung mit 2 434 unabhängigen beobachteten Reflexen, R = 0,047. Gitterabmessungen bei 19°C: a = 1 304,8; b = 996,5; c = 1 339,5 pm, β = 93,75°. Die Verbindung bildet monomere Moleküle mit einer auffällig langen S—Cl-Bindung von 234,2 pm und Abständen SN und PN von 154,6 bzw. 161,6 pm, die Doppelbindungen entsprechen.[SO2(Cl)(NPPh3)]: Raumgruppe P21/n, Z = 4, Strukturlösung mit 2 872 unabhängigen beobachteten Reflexen, R = 0,047. Gitterabmessungen bei 20°C: a = 956,9; b = 1 909; c = 1 002,0 pm, β = 106,06°. Die Verbindung bildet monomere Moleküle mit Abständen S—Cl von 207,1 pm, SN von 154,5 pm und PN von 161,6 pm.[SCl(NPPh3)2]Cl: Raumgruppe P21/c, Z = 4, Strukturlösung mit 5 224 unabhängigen beobachteten Reflexen, R = 0,042. Gitterabmessungen bei 20°C: a = 1 108,6; b = 1 603,8; c = 1 840,5 pm, β = 99,98°. Die Verbindung bildet Ionen [SCl(NPPh3)2]+ und Cl-. Im Kation ist das Schwefelatom ϕ-tetraedrisch koordiniert mit einem langen S—Cl-Abstand von 248,5 pm und SN-Bindungslängen von 154,5 und 156,0 pm.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 20 (1981), S. 413-426 
    ISSN: 0570-0833
    Keywords: Multiple bonds ; Bond theory ; Nitrido ligand ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Numerous nitrido complexes of transition metals show very short metal-nitrogen bond lengths, suggesting M≡N-triple bonds. At present, compounds of this type are being intensively investigated. In particular the molybdenum complexes are considered as model substances for the study of at least an intermediate step of N2-assimilation. This article contains a review of the structure and bonding, as well as syntheses and reactions of these complexes.
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  • 13
    ISSN: 0044-2313
    Keywords: Molybdenum ; Tungsten ; Halogenonitrosyl Complexes ; Syntheses ; IR Spectra ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Halogeno-Nitrosyl Complexes of Molybdenum and Tungsten. Crystal Structures of [Na2(15-Crown-5)2(CH3CN)][MoCl4(NO)2] and [Na(15-Crown-5)]2[MoF4Cl(NO)]MoCl2(NO)2 and WCl2(NO)2, respectively, react with excess sodium fluoride in acetonitrile at room temperature and in the presence of 15-crown-5 to give crystalline mixtures, which consist of the title compounds, respectively of [Na(15-crown-5)]2[WCl4(NO)2] and [Na(15-crown-5)]2[WF4Cl(NO)], and which can be separated by selection. The complexes are characterized by their i.r. spectra, the molybdenum compounds additionally by crystal structure determinations.[Na2(15-crown-5)2(CH3CN)][MoCl4(NO)2]: Space group P21, Z = 2, 5415 independent unique reflexions, R = 0.039. Lattice dimensions at -10°C: a = 984.3, b = 1231.1, c = 1483.0 pm, β = 105.67°. The compound consists of cations [Ne(l5-crown-5)(CH3CN)]+, in which the sodium ion is surrounded by the five O-atoms of the crown ether and by the N-atom of the acetonitrile molecule, as well as of anions, which form an ion pair {Na(15-crown-5)[MoCl4(NO)2]}-. In the in pairs the sodium ion is coordinated by the five oxygen atoms of the crown ether and by two chlorine atoms of the [MoCI4(NO)2]2- unit. The nitrosyl ligands take the cis-position a t the molybdenum atom which is in a distorted octahedrally fashion.[Na(15-crown-5)]2[MoF4Cl(NO)]. Space group C2/c, Z = 4, 1933 independent unique reflexions, R = 0.078. Lattice dimensions at -7O°C: D : 1.585.8, b = 1171.5, c = 1771.5 pm, β = 114.91°. The compound forms an ion triple, in which the sodium ions are linked to five oxygen atoms each of the crown ether molecules, and to two F-atoms of the [MoF4Cl(NO)]2- unit. The F-atom which is arranged in trans-position to the nitrosyl ligand coordinates with both sodium ions; thus an unusual T-shaped arrangement results for this F-atom. The sole terminal F-Atom and the Cl-atom are disordered in two positions.
    Notes: MoCl2(NO)2 bzw. WCl2(NO)2 reagieren mit überschüssigem Natriumfluorid in Acetonitril bei R.T. und Anwesenheit von 15-Krone-5 zu Kristallgemischen, die aus den Titelverbindungen bzw. aus [Na(15-Krone-5)]2[WCl4(NO)2] und [Na(15-Krone-5)]2[WF4Cl(NO)] bestehen, und die sich durch Auslesen trennen lassen. Die Komplexe werden durch ihre IR-Spektren, die Molybdänverbindungen zusätzlich durch Kristallstrukturanalysen charakterisiert.[Na2(15-Krone-5)2(CH3CN)][MoCl4(NO)2]: Raumgruppe P21, Z = 2, 5415 unabhängige beobachtete Reflexe, R = 3,9%. Gitterabmessungen bei -10°C: a = 984,3; b = 1 251,1; c = 1 483,0 pm, β = 105,67°. Die Verbindung besteht aus Kationen [Na(15-Krone-5)(CH3CN)]+, in denen das Natriumion von den fünf O-Atomen des Kronenethers und von dem N-Atom des Acetonitrilmoleküls umgeben ist, sowie aus Anionen, die ein Ionenpaar {Na(15-Krone-5)[MoCl4(NO)2]}- bilden. In ihnen ist das Natriumion durch die fünf O-Atome des Kronenethers und durch zwei Chloratome der [MoCl4(NO)2]2--Einheit koordiniert. Die Nitrosylliganden nehmen die cis-Positionen am verzerrt oktaedrisch koordinierten Molybdänatom ein.[Na(15-Krone-5)]2[MoF4Cl(NO)]: Raumgruppe C2/c, Z = 4, 1933 unabhängige beobachtete Reflexe, R = 7,8%. Gitterabmessungen bei -70°C: a = 1 585,8; b = 1 171,2; c = 1 771,5 pm; β = 114,91°. Die Verbindung bildet ein Ionentripel, in dem die Natriumionen mit je fünf O-Atomen der Kronenethermoleküle und mit zwei F-Atomen der [MoF4Cl(NO)]2--Einheit verbunden sind. Das in trans-Position zum Nitrosylliganden angeordnete F-Atom koordiniert mit beiden Natriumionen, so daß für dieses F-Atom eine ungewöhnliche T-förmige Anordnung resultiert. Das einzige terminal gebundene F-Atom und das Cl-Atom sind in zwei Positionen fehlgeordnet.
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  • 14
    ISSN: 0044-2313
    Keywords: Crown ether complexes of lead ; syntheses ; ir. spectra ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crown Ether Complexes of Lead(II). The Crystal Structures of [PbCl(18-Krone-6)][SbCl6], [Pb(18-Krone-6)(CH3CN)3][SbCl6]2 und [Pb(15-Krone-5)2][SbCl6]2.[PbCl(18-crown-6)][SbCl6] has been prepared in low yield besides [Pb(CH3)2(18-crown-6)][SbCl6]2 by the reaction of Pb(CH3)2Cl2 with antimony pentachloride in acetonitrile solution in the presence of 18-crown-6, forming pale-yellow crystals. The other two title compounds are formed as colourless crystals by the reaction of PbCl2 with antimony pentachloride in acetonitrile solutions in the presence of 18-crown-6 and 15-crown-5, respectively. The complexes were characterized by IR spectroscopy and by crystal structure determinations.[PbCl(18-crown-6)][SbCl6]: Space group P21/c, Z = 8, 5 003 observed unique reflections, R = 0.046. Lattice dimensions at - 80°C: a = 1 386.9; b = 1 642.7; c = 2 172.1 pm, β = 92.95°. The lead atom in the cation [PbCl(18-crown-6)]+ is surrounded in an almost hexagonal-planar construction by the six oxygen atoms of the crown ether and an axially oriented Cl atom.[Pb(18-crown-6)(CH3CN)3][SbCl6]2: Space group P1, Z = 2, 6 128 observed unique reflections, R = 0.076. Lattice dimensions at - 70°C: a = 1 228.0; b = 1 422.9; c = 1 463.2 pm, α = 69.08°; β = 65.71°; γ = 64.51°. In the cation [Pb(18-crown-6)(CH3CN)3]2+ the lead atom is coordinated by the six oxygen atoms of the crown ether and by the three nitrogen atoms of the acetonitrile molecules. The structure determination is restricted by disorder.[Pb( 15-crown-5)2][SbCI6]2: Space group P63/m, Z = 6, 5 857 observed unique reflections, R = 0.059. Lattice dimensions at -70°C: a = b = 2 198.5; c = 1499.4 pm, α = β = 90°, γ = 120°. In the cation [Pb(l5-crown-5)2]2 the lead atom is sandwich-like coordinated by the ten oxygen atoms of the two crown ether molecules. The structure determination is restricted by disorder.
    Notes: [PbCl(18-Krone-6)][SbCl6] entsteht in geringer Menge neben [Pb(CH3)2(18-Krone-6)][SbCl6]2 in Form blaßgelber Kristalle bei der Einwirkung von Antimonpentachlorid auf Pb(CH3)2Cl2 in Acetonitrillösung in Gegenwart von 18-Krone-6. Die beiden übrigen Titelverbindungen werden aus PbCl2 und 18-Krone-6 bzw. 15-Krone-5 durch Reaktion mit Antimonpentachlorid in Acetonitril als farblose Kristalle erhalten. Die Komplexe wurden durch ihre IR-Spektren und durch Kristallstrukturanalysen charakterisiert.[PbCl(18-Krone-6)][SbCl6]: Raumgruppe P21/c, Z = 8, 5 003 beobachtete unabhängige Reflexe, R = 0,046. Gitterkonstanten bei - 80°C: a = 1 386,9; b = 1 642,7; c = 2 172,1 pm, β = 92,95°. In dem Kation [PbCl(18-Krone-6)]+ ist das Pb-Atom nahezu coplanar mit den sechs O-Atomen des Kronenethers angeordnet, während das Chloratom kovalent und axial mit dem Pb-Atom verbunden ist.[Pb(18-Krone-6)(CH3CN)3][SbCl6]2: Raumgruppe P1, Z = 2, 6 128 beobachtete unabhängige Reflexe, R = 0,076. Gitterkonstanten bei - 70°C: a = 1 228,0; b = 1 422,9; c = 1 463,2 pm, α = 69,08°; β = 65,71°; γ = 64,51°. In dem Kation [Pb(18-Krone-6)(CH3CN)3]2+ ist das Bleiatom neunfach durch die sechs O-Atome des Kronenethers und durch drei N-Atome der Acetonitrilmoleküle koordiniert. Die Genauigkeit der Strukturbestimmung ist durch Fehlordnung beeinträchtigt.[Pb(15-Krone-5)2][SbCl6]2: Raumgruppe P63/m, Z = 6, 5 857 beobachtete unabhängige Reflexe, R = 0,059. Gitterkonstanten bei - 70°C: a = b = 2 198,5; c = 1 499,4 pm, α = β = 90°, γ = 120°. In dem Kation [Pb(15-Krone-5)2]2+ ist das Bleiatom zehnfach sandwichartig durch die O-Atome der beiden Kronenethermoleküle koordiniert. Die Genauigkeit der Strukturbestimmung ist durch Fehlordnung beeinträchtigt.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 31 (1992), S. 955-978 
    ISSN: 0570-0833
    Keywords: Transition metals ; Nitrido ligand ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the past decade new syntheses and numerous structural determinations have enlivened studies in the still relatively young field of nitrido-transition-metal complexes. Aside from the terminal function of the nitrido ligand M≡N:, this group also occurs as linear μ2-bridging ligand in symmetric and asymmetric coordination; examples are known with almost right-angled bridge function; and, finally, it also functions as μ3-bridging ligand. Accordingly, the fresh impulses given to synthetic chemistry by nitrido complexes are also many-sided: such complexes are used, inter alia, for the preparation of phosphaniminato and thionitrosyl complexes as well as for the synthesis of metallaheterocycles of the type MN3S2 and MN3P2 with delocalized π-systems. In technetium chemistry complexes with terminal nitrido group are employed as radiopharmaceuticals, and, owing to the strong trans influence of the M≡N: group, nitrido complexes of molybdenum are suitable as catalysts in olefin metathesis. Finally, nitrido complexes are also of wide interest in theoretical studies.
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