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  • 1
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The surface product formed in the reaction between TiCl3 and Al(CH3)3 has been studied. Stoichiometric data, CH3/CD3 exchange, and infrared spectra permit the conclusion that the surface product is essentially a compound having the formula A model structure is proposed for this compound, valid for the 001 face of α-TiCl3. In it the titanium and chlorine atoms maintain the positions which they occupy in the α-TiCl3 lattice. One of the methyl groups protrudes from the surface whereas the other occupies the chlorine vacancy created during the reaction in the chlorine surface layer. A different sterism of the methyl groups is compatible with the experimental result that half of the methyl groups are very easily exchanged whereas the other half are not touched by the exchanging agent. According to this model it has to be assumed that the titanium atoms in the 001 plane, by far the largest face of the α-TiCl3 crystal, are not accessible. A similar model, loading to equivalence conclusions is proposed for β-TiCl3. The infrared spectra of Al(CH3)3, Al(CD3)3, AlCl(CH3)2, AlCl(CD3)2, AlCl2CH3, AlCl2CD3, TiCl3CH3, TiCl3CD3, Hg(CD3)2, and Zn(CD3)2 are discussed. Spectra of surface products formed on interaction of some of these compounds with TiCl3 are given.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1905-1916 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between α-TiCl3 and AlMe3 at 65°C. in the absence of solvent was studied by a method which gives information about the early stages of the reaction. The results obtained give evidence for a sequence of consecutive reactions and show that the first of these is a fast partial alkylation of the α-TiCl3 surface. The mechanism of formation of methane in the last step of the reaction is discussed in detail.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1917-1926 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The following reactions, carried out in the absence of solvents, has been studied: α-TiCl3 + Al(CH3)3 at 20°C., β-TiCl3 + Al(CH3)3 at 65°C., α-TiCl3 + Al(CH3)2Cl at 20 and 65°C., and α-TiCl3 + Al(C2H5)3 between 30 and 65°C. It appears that a general reaction mechanism, such as discussed in the preceding paper of this series, applies to all these reactions between TiCl3 and aluminum alkyls. The differences in overall stoichiometry between some of these systems may be linked to differences in stability of the intermediate Ti—C bonds. In the case of α-TiCl3 + Al(CH3)2Cl, alkylation is probably accompanied by fixation of the AlCH3Cl2 on the nonvolatile product.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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