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  • 1
    Electronic Resource
    Electronic Resource
    Oxford [u.a.] : International Union of Crystallography (IUCr)
    Acta crystallographica 57 (2001), S. 195-196 
    ISSN: 1600-5759
    Source: Crystallography Journals Online : IUCR Backfile Archive 1948-2001
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: In the title compound, C25H40N2P+·Cl−, the cation structure (at 150 K) is intermediate between those of the iminophosphorane and the ylide, consistent with delocalization of the positive charge between the P and the adjacent N atoms. The cation and anion are linked by a strong N—H...Cl hydrogen bond.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0887-624X
    Keywords: metathesis ; regioselective polymerization ; 7-alkylnorbornenes ; ab initio MO Calculations ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ring-opened metathesis polymers of 7-phenylnorbornadiene and benzonorbornadiene have been prepared using a variety of catalysts based on Ru, Os, Ir, W and Mo chloride salts and complexes. Detailed 13C and 1H NMR spectra of these materials and their corresponding hydrogenated derivatives have been obtained and analysed for information concerning tacticities and fractions of cis double bonds (σc). The behaviour of 7-phenylnorbornadiene is similar to that of 7-methylnorbornadiene in that a strong preference for the anti over the syn mode of monomer insertion is observed in contrast to 7-tert-butoxynorbornadiene which shows little or no regioselectivity. Pronounced effect on σc are also observed using the OsCl3 catalyst as expected from previous experience of ring-opening metathesis polymerization (ROMP) systems containing chelating dienes and this catalyst. Weaker effects of this type due to complexation of monomer as a spectator ligand are also indicated for the polymerization of benzonorbornadiene; these are also compared to the effects of using Michael acceptor additives in metathesis systems.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 194 (1993), S. 2907-2922 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ring-opened metathesis polymers of 7-methylnorbornadiene (1) have been synthesized with cis main-chain double bond contents ranging from 20 to 97% using several initiators; their microstructures have been examined in detail using 13C NMR spectroscopy. The result show that polymerization from the anti-exo orientation is greatly favoured over the syn-exo mode. A nonbonded repulsion energy of 6-8 kJ · mol-1 between the syn-7-methyl group and the double bond is estimated. The microstructural features also resemble those for polymers of the anti- and syn-7-methylnorbornenes, in contrast to poly(norbornadiene) itself and to poly(norbornene), in that the splitting of a given resonance due to tacticity effects is of the same order as splittings due to neighbouring double bonds. Cis double bond contents and tacticities using different catalysts agree well with those expected from previous work with norbornadiene and several methyl-substituted norbornenes, respectively, as monomers. The previous surprising observation that there is significantly less or no discrimination between the syn- and anti-orientations in polymerizing 7-tert-butoxy- and 7-acetoxynorbornadiene is discussed and is attributed to a pseudo [3 + 2] transition state replacing the normal one for [2 + 2] metallacyclobutanation. In the [3 + 2] mode a lone pair of electrons on the oxygen acts in conjunction with the π pairs of the C=C and [Mt]=C moieties. The net effect is to lower the energy barriers for the [2 + 2] cycloaddition and the reverse step. The same explanation, rather than chelation, is also believed to be correct for the beneficial effect on the metathesis polymerization of the 7-oxa group in several substituted 7-oxanorbornenes and 7-oxanorbornadienes when compared to the corresponding 7-methylene monomers.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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