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  • (Phosphane)gold(I) complexes  (2)
  • Phosphane boranes
  • Ylides
  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Monatshefte für Chemie 111 (1980), S. 1233-1244 
    ISSN: 1434-4475
    Schlagwort(e): Metallocycles ; Organometallic compounds of do and d10 metals ; Phosphane boranes ; Phosphorus Ylides ; Ylide complexes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Dehydrohalogenation and metallation of boranato-bis-trimethylphosphonium salts (1), using two equivalents of a lithiumalkyl in tetrahydrofuran, leads to a solvated organolithium reagent H2B[(CH3)2PCH2]2Li (3) which can be converted into a 1:1n1-complex with tetramethylethylenediamin (4).3 reacts with anhydrous metal(II) halides to form spirocyclic coordination compounds of the type H2B[(CH3)2PCH2]2 M[CH2P(CH3)2]2BH2 (5–9,M=Be, Mg, Zn, Cd, Hg). The reaction of [(CH3)3PBH2P(CH3)3]Br (1) with lithium tetramethylmetalates Li[M(CH3)4],M=Al, Ga, on heating in the absence of a solvent affords the metallocycles H2B[(CH3)2PCH2]2 M(CH3)2 (10, 11) with evolution of methane. The products can be sublimed from the reaction mixture. The proposed structures of the new compounds, with tetrahedrally coordinated central atoms and strong covalent metal-carbon interactions, are supported by mass, IR and1H,7Li,11B,13C, and31P NMR spectra. Compound9 represents a rare case of a tetracoordinate organomercurial, compound5 is the first nonionic tetraalkylberyllate.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 217-219 
    ISSN: 0009-2940
    Schlagwort(e): Gold compounds ; (Phosphane)gold(I) complexes ; Clusters ; P Ligands ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Phenylene-1,2-bis(phosphane) reacts with two mole-equivalents of tris[(triphenylphosphane)gold(I)]oxonium tetrafluoroborate in dichloromethane at -78°C to give high yields of a hexanuclear complex {C6H4]P(AuPPh3)3]2}2+ · 2 BF-4 (1). The variable-temperature 31P{1H}-NMR spectra of the product in CD2Cl2 at - 80°C are compatible with a static structure featuring three Ph3PAu units associated with each of the two C6H4P2 phosphide functions, as derived from a clear doublet/quartet pattern. At 50°C in CDCl3, however, there is rapid intramolecular scrambling of these Ph3PAu units, which gives rise to a triplet/septet pattern with the J(P,P) value reduced to exactly one half of the value at the low temperature limit.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 1599-1603 
    ISSN: 0009-2940
    Schlagwort(e): Silicon compounds ; Ylides ; NMR, 13C, 17O, 29Si ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two series of aminophosphonium ylides with reactive alkoxychlorosilyl substituents (R2N)3P=CHSi(OR')2Cl (1-8, R = Me, Et/R' = Me, Et, iPr, tBu) have been prepared by reaction of the aminophosphonium ylides (R2N)3P = CH2 with the corresponding dialkoxydichlorosilanes Cl2Si(OR')2. Substituent effects have been investigated by heteronuclear solution NMR studies of the nuclei 1H, 13C, 15N, 17O, 29Si, and 31P. These studies show an alternating shielding effect along the C-O-Si-C backbone. Further reactions of the chlorosilylated ylides with the aminomethylenephosphorane (Me2N)3P=CH2 lead to the formation of the bis-ylidic compounds [(Me2N)3P=CH]2Si(OR')2 (9, 10), which are also available in one-pot syntheses. The molecular structure of [(Me2N)3P=CH]2Si(OiPr)2 (9) has been confirmed by single-crystal X-ray diffraction. In the crystal the molecules have two ylidic carbon centers with planar configuration, which are bridged by a nearly tetrahedral silicon atom. Short P-C and Si-C distances indicate a stabilizing effect of the carbanionic centers.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 901-905 
    ISSN: 0009-2940
    Schlagwort(e): Gold sulfide complexes ; Gold thiolates ; (Phosphane)gold(I) complexes ; Digoldsulfonium salts ; Digoldchloronium salt ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 1,4-Bis(diphenylphosphanylmethyl)benzene (1) was converted into its bis[chlorogold(I)] complex [1 · (AuCl)2] upon treatment with two equivalents of chloro(dimethyl sulfide)-gold(I). The reaction of 1 · (AuCl)2 with one equivalent of silver tetrafluoroborate afforded a cyclic di[gold(I)]chloronium tetrafluoroborate [1 · Au2Cl+ BF-4]. Substitution of chloride in 1 · (AuCl)2 by sodium methanethiolate in wet chloroform, gave the bis[methylthiogold(I)] complex 1 · (AuSMe)2], while with sodium sulfide a cyclic complex 1 · Au2S was obtained. Reaction of 1 · (AuCl)2 with two equivalents of AgBF4 followed by treatment with diphenyldisulfide or sodium methanethiolate yielded the cyclic methyl/phenylsulfonium tetrafluoroborates 1 · Au2SPh+ BF-4 and 1 · Au2SMe+BF-4, respectively. All compounds were identified on the basis of their analytical and spectroscopic data. The crystal structures of 1 · (AuCl)2, 1 · (AuSMe)2, and 1 · Au2S have been determined. The Au2S complex has a cyclic structure with a narrow Au-S-Au angle of 86.7(1)° indicating a significant intraannular Au…Au interaction.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 22 (1983), S. 907-927 
    ISSN: 0570-0833
    Schlagwort(e): Phosphorus ylides ; Coordination modes ; Transition metals ; Ylides ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Phosphorus ylides are not only classical reagents in organic chemistry, but also play an increasingly important role as novel components in organometallic compounds. These metallic “ylide complexes” are either synthesized from “preformed ylides” and coordination compounds by addition or substitution, on the building block principle, or they are formed, in sometimes complicated reactions, from phosphanes, metal complexes, and C1 substrates in the coordination sphere of the metals. The resulting metal-carbon bonds are greatly modified in their properties by the immediate presence of the phosphonium center and often belong to the most stable of M-C structural units. The metal can come from any group of the periodic table, including the lanthanoids and actinoids. Numerous preparative and structural studies are gradually enabling us to gain an overall picture of the scope of this area of research.
    Materialart: Digitale Medien
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