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The Active Species in Homogeneous Ziegler-Natta Catalysts for the Polymerization of EthyleneExtended version of a lecture delivered at the “Makromolekulares Kolloquium”, Freiburg, in March 1967. (1967)

Henrici-olivé, G. ; Olivé, S.

Weinheim : Wiley-Blackwell

Angewandte Chemie International Edition in English 6 (1967), S. 790-798

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ISSN: 0570-0833

Schlagwort(e): Ziegler-Natta catalysts ; Catalysis ; Polymerization ; Polyethylene ; Chemistry ; General Chemistry

Quelle: Wiley InterScience Backfile Collection 1832-2000

Thema: Chemie und Pharmazie

Notizen: Cp2TiCl2 and Cp2TiEtCl (Cp = cyclopentadienyl, Et = ethyl), in combination with aluminum alkyls, have been studied as model catalyst systems for the polymerization of ethylene in toluene. The activity of these systems resides in the presence of a complex molecule involving an alkylated Ti(IV) and an alkylated Al species, linked together by chlorine bridge bonds. The environment of the Ti is of octahedral symmetry with one vacant site available for the coordination of ethylene. The bridged Al-alkyl causes a destabilization of the Ti-alkyl bond (“trans effect”), thus rendering it active for polymerization. The reduction Ti(IV) → Ti(III), inevitable in these systems, involves the irreversible change from octahedral to tetrahedral symmetry with loss of the catalytic activity. Polymerization and reduction are supposed to occur at the same catalyst site. Magnetic methods (susceptibility and EPR) as well as the kinetics of polymerization were used in the investigation of these catalyst systems.

Zusätzliches Material: 15 Ill.

Materialart: Digitale Medien

URL: http://dx.doi.org/10.1002/anie.196707901

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Digitale Medien

Nickel-Catalysed Reactions of Allyl Halides and Related Compounds (1967)

Chiusoli, G. P. ; Cassar, L.

Weinheim : Wiley-Blackwell

Angewandte Chemie International Edition in English 6 (1967), S. 124-133

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ISSN: 0570-0833

Schlagwort(e): Allyl halides ; Catalysis ; Nickel ; Chemistry ; General Chemistry

Quelle: Wiley InterScience Backfile Collection 1832-2000

Thema: Chemie und Pharmazie

Notizen: Allyl compounds react with carbon monoxide, or with carbon monoxide and acetylene, in the presence of tetracarbonylnickel as catalyst. These catalysts are involved also in coupling reactions and addition reactions of activated olefins and ketones. Reactions of this type can be used for the preparation of unsaturated aliphatic acids, esters, nitriles, hydrocarbons, alicyclic ketones, keto acids, keto esters, diketones, lactones, phenols, and other compounds. The reactions proceed via π-allylnickel complexes.

Zusätzliches Material: 5 Tab.

Materialart: Digitale Medien

URL: http://dx.doi.org/10.1002/anie.196701241

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