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  • General Chemistry  (44)
  • Phosphanorbornadiene  (2)
  • 2-(2-Pyridyl)phosphinines  (1)
  • 1
    ISSN: 0009-2940
    Schlagwort(e): 2-(2-Pyridyl)phosphinines ; 2,2′-Biphosphinines ; Transition metals ; Biphosphinine chelates ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis and coordination chemistry of 2-(2-pyridyl)-phosphinines and 2,2′-biphosphinines are reviewed. A noteworthy series of homoleptic complexes of 4,4′,5,5′-tetramethyl-2,2′-biphosphinine (tmbp) with Cr(0), Mo(0), Wo(0) and Ni(0) are described. A [Cu(bpy)(tmbp)]+ cationic polymer has been characterized by X-ray analysis. Ruthenium, manganese and rhenium chelates were also obtained. With Mn2(CO)10, a (tmbp)-Mn2(CO)6 complex is formed where tmbp acts as an eight electron donor.
    Materialart: Digitale Medien
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  • 2
    ISSN: 1434-193X
    Schlagwort(e): Phosphole ; Phosphanorbornadiene ; Stille cross-coupling ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of alkynylstannanes with 1-phenyl-3,4-dimethylphosphole at 150 °C affords the corresponding 2-stannyl-1-phosphanorbornadienes (2a, b), in fair yield. Oxidation under mild conditions affords the corresponding phosphane oxides (3a, b), whereas more drastic conditions (H2O2, 15% in toluene at 80 °C) induce the oxidative cleavage of the P-CH2 bond of the bridge to give a bicyclic phosphinate such as 4. Treatement of 4 by iodine leads to a tin → iodine exchange. The X-ray crystal structure analysis of the resulting 1-phospha-2-oxabicyclo[2.2.2]octa-5,7-diene 1-oxide confirms the functionalisation at the α-position and the relief of ring strain taking place upon insertion of oxygen into the P-CH2 bond of the norbornadiene. The 2-stannyl-1-phosphanorbornadiene 1-oxides (3a, b) readily undergo tin → iodine exchange. The resulting 2-iodo derivatives (6a, b) can be cross-coupled with 2-furyl-, 2-thienyl-, 2-pyrrolyl-, phenylethynyl-, and vinyl-tributylstannanes to give the corresponding 2-functional 1-phosphanorbornadiene 1-oxides in excellent yields (80-95%)
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1434-193X
    Schlagwort(e): Phosphorus heterocycles ; Nitrogen heterocycles ; Phosphinines ; Phosphaalkynes ; [4 + 2] Cycloadditions ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: tert-Butylphosphaethyne (2) undergoes a Diels-Alder reaction with the 1,3,2-diazaphosphinine 1 at room temperature to furnish the diazadiphosphabarrelene 3. In the presence of an excess of 2 in toluene under reflux compound 3 experiences elimination of a molecule of pivalonitrile to afford the 1-aza-2,4-diphosphinine 5 which, in turn, reacts with a further equivalent of 2 to form the transient azatriphosphabarrelene 6. Formation of the final product, the stable tetraphosphatetracyclic compound 4, is the result of a homo Diels-Alder reaction between 6 and yet another equivalent of 2. The structure of 4 has been confirmed by an X-ray crystallographic analysis of its pentacarbonyltungsten complex 7. As a consequence of the high steric overcrowding in 4, complexation occurs exclusively at its phosphaalkene phosphorus atom. The reactivity of 2 towards the four functionally substituted 1,2-azaphosphinines 8a-d has also been examined. At room temperature smooth [4 + 2] cycloaddition reactions proceed to yield the azadiphosphabarrelenes 9a-d. While thermolyses of the barrelenes 9a-c in toluene under reflux lead exclusively to the starting compounds 8a-c by a [4 + 2] cycloreversion process with concomitant elimination of 2, pyrolysis of 9d under the same conditions furnishes the 1,3-diphosphinine 10, also unambiguously identified by analysis of its tpentacarbonyltungsten complex 11.
    Materialart: Digitale Medien
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  • 4
    ISSN: 1434-1948
    Schlagwort(e): Arene complexes ; Catalysis ; Diazadiene complexes ; Iron ; Metal vapour ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two different routes to novel [(diene)(η6-2,6-dimethylpyridine)Fe] complexes are reported, both of which utilize metal vapour reactions. The presence of two small substituents on the 2,6-position of pyridine is essential for the η6-coordination of the heterocycle. Investigations on the reactivity and stability of the [(diene)(η6-arene)Fe] complexes are presented, including those of the benzene, phosphinine, and pyridine derivatives. These investigations give some hints to the relevant factors for determining the interaction between an iron atom and a π-coordinated neutral arene ligand, and their modification by a nitrogen or a phosphorus atom. Selective substitution of the 1,5-cyclooctadiene (COD) ligand of [(COD)(η6-arene)Fe] complexes by some 1,4-diaza-1,3-diene (DAD) derivatives is possible in the case of the benzene or phosphinine arene ligands, and [(DAD)(η6-arene)Fe] complexes are formed, but all DAD derivatives tested so far cause the complete disintegration of [(COD)(η6-2,6-dimethylpyridine)Fe]. [(DAD)(η6-arene)Fe] complexes exhibit a catalytic potential, which was evaluated by experiments on the catalytic cyclodimerization of 1,3-butadiene in the presence of [(Et2AlOEt)2] as a co-catalyst. This reaction yields up to 92% of 1,5-cyclooctadiene, and an almost quantitative butadiene conversion is possible in the presence of less than 0.1% of the catalyst. Structural investigations on [(N,N′-bis(cyclohexyl)ethylenediimine)(η6-toluene)Fe] 5a reveal some details of the Fe-DAD interaction. An effective electron back-donation from occupied iron d-orbitals into the π*-LUMO of the DAD is indicated.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2233-2241 
    ISSN: 1434-1948
    Schlagwort(e): Phosphorus ; Heterocycles ; Phosphinines ; Gold ; Cycloadditions ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The coordination behaviour of 2,6-disilyl-substituted phosphinines towards gold(I) has been examined. The reaction of the bis(trimethylsilyl)phosphinine 1 with [AuCl(SMe2)] gives the corresponding AuCl derivative 2. X-ray crystal structure analysis reveals that the aromaticity of the phosphinine ring is slightly reduced as a result of the poor π-back bonding ability of the AuCl fragment. The same phenomenon is observed in the cationic complex [Au(1)2][GaCl4] (3) which was readily prepared by reaction of two equivalents of 1 with [AuCl(SMe2)] followed by treatment with GaCl3 at low temperature. Reaction of 2,6-bis(phenylethynyldimethylsilyl)phosphinine (4) with the same precursor leads similarly to the complex [AuCl(4)] (5). Interestingly, this complex dimerizes upon crystallization to give the bis(phosphabarrelene) complex 6, also structurally characterized. The formation of 6 results from a [4 + 2] cycloaddition between one alkynyl group of each phosphinine with the other phosphinine subunit. The formation of the cationic complex [Au(4)][GaCl4] (8) occurs under classical conditions but it disproportionates to give the cationic complex [Au(4)2][GaCl4] (9) and colloidal gold deposition. The formation of 9 has been ascertained by treating 8 with one equivalent of ligand 4. Additionally, 9 can also be obtained in a straightforward fashion by treating two equivalents of 4 with [AuCl(SMe2)] followed by treatment with GaCl3 at low temperature. The structure of 9 has been elucidated. Despite a particular arrangement of the alkyne groups which encapsulate the gold coordination sphere, no gold-alkyne interactions are visible.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 1091-1097 
    ISSN: 1434-193X
    Schlagwort(e): Phosphanorbornadiene ; Allylic metalation ; Allylic bromination ; BIPNOR dioxide ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: -3-Methyl-substituted 1-phosphanorbornadiene oxides or sulfides such as 1a,b are either metalated by a strong base (n-BuLi or LDA) or brominated by NBS at the methyl substituent. The reaction of the resulting delocalised carbanions 2a,b takes place either at C-2 (H+, MeI) or at the methylene group (Me3SiCl, ClPPh2, I2). In the last case, γ-functional (5a,b or 6a,b) or bridged (7) phosphanorbornadienes are obtained. Similarly, the reaction of 3-bromomethyl-1-phosphanorbornadiene oxides such as 8 with nucleophiles [NaCH(CO2Me)2, PhO-, Me2NH, PhCH2NH2] yields the corresponding γ-functional phosphanorbornadienes 9-12. This chemistry has also been applied to the BIPNOR dioxide 13.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 7
    ISSN: 0947-6539
    Schlagwort(e): asymmetric catalysis ; hydrogenations ; palladium ; phosphorus ligands ; rhodium ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Optically active phosphorus ligands are widely used in homogeneous asymmetric catalysis. However, among the numerous available structures of this type, the subclass of optically active bisphosphines with at least one chiral phosphorus atom is rather underdeveloped. A bisphosphine with two chiral, nonracemizable bridgehead phosphorus centers, (meso,d/l)-2,2′,3,3′-tetraphenyl-4,4′,5,5′-tetramethyl-6,6′-bis-1-phosphanorborna-2,5-dienyl (BIPNOR), can be obtained by thermolysis of 1,1′-bisphospholyl with diphenylacetylene. Here, we report the resolution of the d/l isomer by means of a chiral palladium complex to give the two optically active forms of BIPNOR. We then investigate the catalytic properties of BIPNOR, incorporated in RhI and RuII catalysts for the hydrogenation of olefins and ketones and in a PdII catalyst for asymmetric alkylation reactions. BIPNOR is shown to give good results in these catalytic reactions.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 109 (1997), S. 2460-2462 
    ISSN: 0044-8249
    Schlagwort(e): Homogene Katalyse ; Palladium ; Platin ; P-Liganden ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 109 (1997), S. 117-119 
    ISSN: 0044-8249
    Schlagwort(e): Heterocyclen ; Phosphor ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 10
    ISSN: 0044-8249
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Im Vergleich zur Chemie anderer wohlbekannter Elektronenmangelverbindungen wie der Carbene, Silylene und Nitrene ist die Chemie der Phosphinidene RP: äußerst wenig erforscht. Ein kritisches Studium der Literatur zeigt, daß als wahrscheinliche Ursachen sowohl eine schlechte Zugänglichkeit dieser Spezies als auch ein ihnen eigener Mangel an Reaktivität anzunehmen sind. Die Ergebnisse von Rechnungen deuten darauf hin, daß es möglich ist, durch Komplexierung mit Übergangsmetall-Komplexfragmenten wie M(CO)5 (M = Cr, Mo, W) die Elektrophilie der Phosphinidene zu erhöhen und ihren Singulett-Zustand zu stabilisieren. Die entsprechenden Komplexe mit terminalen Phosphiniden-Liganden [RP=M(CO)5] zeigen eine reichhaltige und vielseitige Chemie, die häufig der der Singulett-Carbene entspricht. Herstellen lassen sich kurzlebige Phosphiniden-Komplexe durch thermische Zersetzung von 7-Phosphanorbornadien-Komplexen; ihre Stabilisierung jedoch ist eine noch nicht bewältigte Aufgabe.
    Materialart: Digitale Medien
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