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  • 1
    Digitale Medien
    Digitale Medien
    Über die Reaktion von tert-Butyl(tert-butylimino)phosphan mit tert-Butyl-(tert-butylimino)boran (1988)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 565-568 
    Details
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: On the Reaction of tert-Butyl(tert-butylimino)phosphane with tert-Butyl(tert-butylimino)boraneContrary to the [2 + 2] cycloaddition reaction of aminoiminophosphanes with iminoboranes, the title compounds react to yield the heterocyclic products 7 and 9, the structures of which were determined by means of spectroscopic methods and, in the case of 9, additionally by X-ray structural analysis. Further investigations on the reaction mechanism suggest that the first step of the reaction sequence is an oxidative [2 + 1] cycloaddition of the iminophosphane 3 to 2.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19881210328
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  • 2
    Digitale Medien
    Digitale Medien
    Methylenphosphanyl-Komplexe von Chrom, Molybdän, Wolfram, Eisen und Nickel: Synthese und ReaktionenHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1299-1309 
    Details
    ISSN: 0009-2940
    Schlagwort(e): Methylenephosphanyl complexes ; Phosphenium complexes ; Phosphavinylidene complexes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Methylenephosphanyl Complexes of Chromium, Molybdenum, Tungsten, Iron and Nickel - Synthesis and ReactivityHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet.The reaction of the functionalized P/C double bond systems X - P=C(R)SiMe3 [R=SiMe3 and X=Cl (1a), Cp* (5a) or R=Ph and X=Br (1b), Cp* (5b)] with alkali carbonylmetallates or carbonyl complexes of group 6, 8, and 10 metals leads to the formation of the transition metal-substituted phosphaalkenes [{M} - P=C(R)SiMe3 3a - j and 4a - i], in which the P - C fragment acts as a one-electron donor. Depending on the nucleophilicity of the transition metal anion used, but also on the methylene carbon substituents [1a: (SiMe3)2: 1b: (Ph)1-SiMe3], a different stability of the (methylenephosphanyl)1-metal complexes is observed, which results in a broad spectrum of reactivities. As demonstrated by the reactions of the (methylenephosphanyl)metal complexes with sulfonic acid derivatives (10a - c), diverse transition metal complexes (11a - c), as well as chalcogenes (14a - c, 15), a change in the reactivity is observed, indicating a transition from an olefinic to a carbenic character of the methylenephosphane. In comparison to the phenyl-substituted derivatives 4a - i the bis(trimethyl)1-substituted species 3a - j exhibit an increased reactivity. This is reflected in the easy decarbonylation of 3a - d to the phosphavinylidene complexes 12a - d.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19931260606
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  • 3
    Digitale Medien
    Digitale Medien
    Synthese und Charakterisierung stabiler Bis(phosphonio)isophosphindolylium-Carbonylmetallate und eines kationischen Bis(phosphonio)isophosphindolylium-Gold-KomplexesHerrn Professor Alfred Schmidpeter zum 65. Geburtstag gewidmet. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 259-266 
    Details
    ISSN: 0009-2940
    Schlagwort(e): Bis(phosphonio)isophosphindolylium cation ; Gold complexes ; Bis(phosphonio)isophosphindolylium carbonylmetallates ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis and Characterisation of Stable Bis(phosphonio)isophosphindolyliumcarbonylmetallates and a Cationic Bis(phosphonio)isophosphindolylium-Gold ComplexHerrn Professor Alfred Schmidpeter zum 65. Geburtstag gewidmet.Reaction of 1,3-bis(triphenylphosphonio)isophosphindolylium bromide, [L+][Br-] (1a), with Tl[Co(CO)4], Na[MoCp-(CO)3], or Na[WCp(CO)3] (5a-c) yields the corresponding ionic isophosphindolylium-carbonylmetallates, 6a-c. Whereas 1a fails to react with neutral metal carbonyls, a mixture of ionic complexes of the type [LAuX+][AuYZ-] (7a, X, Y, Z = Cl or Br) is formed by reaction with two equivalents of AuCl. Treatment of AuCl with the triflate [L+][OTf-] (1b), which is accessible from 1a via anion metathesis, furnishes [LAuCl+][OTf-] (7b). Both the carbonylmetallate 6c and the complex 7b have been characterized by X-ray structure analyses. 7b displays enhanced reactivity as compared to 1b towards MeOH and H2O, forming the addition products 8 and 9a, b, the latter existing as two different diastereomers. Reactions of 7b with LiF, (Me2N)3P=O, and (Et2N)2C=NH), respectively, proceed via ligand exchange to yield equilibrium mixtures containing the cations [L+] and [LAuCl+].
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19951280309
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  • 4
    Digitale Medien
    Digitale Medien
    Reactions of diaminophosphenium and 1,3,2-diazaphospholenium triflates with silver saltsDedicated to Professor Dr. Marianne Baudler on the occasion of her 75th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 465-469 
    Details
    ISSN: 0009-2940
    Schlagwort(e): Phosphenium cations ; Silver complexes ; 31P, 109Ag NMR shift correlation ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reaction of bis(diisopropylamino)phosphenium triflate (1[CF3SO3]) with silver salts AgY [Y- = CF3CO2- (2a), CF3-SO3- (2b), CH3CO2- (2c)] affords neutral complexes [{(iPr2N)2(Y)P} Ag(OSO2CF3)] (3a-c). While 3a, c are stable up to ambient temperature, 3b is only stable at low temperature and in equilibrium with the cation 1. The constitution of 3a-c was derived from multinuclear (1H, 13C, 31P, 109Ag) NMR spectra. Compound 3a was further studied by X-ray single-crystal diff ractommetry which showed the presence of dimeric units with μ2-bridging triflate ligands and three-coordinate silver atoms with a planar T-shaped coordination geometry. Reaction of 4-chloro-1,3-bis(2,6-dimethylphenyl)-1,3,2-diazaphospholenium triflate (4[CF3SO3]) with 2a, c affords equilibrium mixtures whose 31P- and 109Ag-NMR spectra suggested the presence of silver complexes 5a, c with constitutions similar to those of 3a, c besides unreacted cation 4. No reaction was observed between 4[CF3SO3] and 2b. A common mechanism accounting for the different outcome of the individual reactions will be discussed.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19961290416
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  • 5
    Digitale Medien
    Digitale Medien
    [Bis(phosphonio)isophosphindolide]silver ComplexesDedicated to Professor Dr. Rolf Appel on the occasion of his 75th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 337-345 
    Details
    ISSN: 0009-2940
    Schlagwort(e): Bis(phosphonio)isophosphindolide cations ; Silver complexes ; 31P NMR ; 109Ag NMR ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The outcome of reactions of bis(phosphonio)isophosphindolide salts 1[X] and 6[X] (X- = Cl-, Br-, CF3SO3-) with silver salts AgY (Y- = CF3SO3-, CF3CO2-, CH3CO2-, 1/2 SO4-) depends strongly on the available anions X, Y. If X-, Y- = CF3SO3-, both mononuclear and dinuclear silver complexes are formed which exhibit either μ1,μ1(P) or μ2,η1(P) coordination of the cations 1, 6 to one or to both metals. In solution, dynamic equilibria between both types of products and free 1, 6 were detected by 31P-NMR spectroscopy. Mononuclear (4a, 7) and dinuclear (5a, 8) complexes were isolated as solvates with CHCl3 or THF. If X-, Y- = CF3CO2, only equilibrium mixtures between the free ligands and silver complexes and no isolable products were obtained. 31P-NMR investigations revealed a preference for the formation of dinuclear complexes. Anion metathesis and precipitation of AgX were observed for X- = Cl-, Br-. No coordination of 1, 6 to Ag+ took place in the case of Y- = CH3CO2-, SO42-. The formed complexes were characterised in solution by 31P- and in part by 109Ag-NMR spectroscopy. Complexes 7, 8 were further studied by single crystal X-ray diffraction which revealed the presence of a THF molecule coordinated to silver in both cases. The μ2-coordinated cation 1 is the only bridging ligand in 8, whereas the presence of additional μ2-CF3CO2 ligands was deduced from the results of 31P,31P EXSY measurements in the case of the trifluoroacetato complexes.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19961290315
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  • 6
    Digitale Medien
    Digitale Medien
    Synthese, Struktur und Reaktivität eines 2,4-Diphosphino-1,3-diphospha-2,4-disilacyclobutansProfessor Herbert W. Roesky zum 60. Geburtstag gewidmet (1995)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 1951-1957 
    Details
    ISSN: 0044-2313
    Schlagwort(e): diphosphadisilacyclobutanes ; x-ray crystallography ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthesis, Structure, and Reactivity of a 1,3-Diphosphino-2,4-diphospha-1,3-disilacyclobutanePentamethylcyclopentadienyltrichlorosilane reacts with Li[Al(PH2)4] to give the stable 1,3-diphosphino-2,4-diphospha-1,3-disilacyclobutane 4. Treatment of 4 with Lithium alkyls affords the Lithium phosphide 5 via regiospecific metalation of a ring phosphorus atom, and reaction with t-Bu2Hg proceeds via oxidative P—P bond formation to yield the 1,4-disila-2,3,5,6-tetraphospha-bicyclo[2,1,1]-hexane 6. Cleavage of pentamethylcyclopentadiene is observed during thermolysis of 4 at 200°C. 4-6 were characterised by NMR-spectroscopy, and 4 by an additional crystal structure determination.
    Notizen: Pentamethylcyclopentadienyltrichlorsilan reagiert mit Li[Al(PH2)4] zum stabilen 1,3-Diphosphino-2,4-diphospha-1,3-disilacyclobutan 4. Umsetzungen von 4 mit Lithiumalkylen liefern unter regiospezifischer Metallierung eines Ring-Phosphoratoms das entsprechende Lithiumphosphid 5, während bei der Reaktion mit t-Bu2Hg unter oxidativer P—P-Verknüpfung das 1,4-Disila-2,3,5,6-tetraphospha-bicyclo[2,1,1]-hexan 6 erhalten wird. Bei der thermolytischen Zersetzung von 4 wird bei 200°C die Abspaltung von Pentamethylcyclopentadien beobachtet. 4-6 werden durch NMR-spektroskopische Untersuchungen, 4 zusätzlich durch eine Röntgenstrukturanalyse charakterisiert.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/zaac.19956211120
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