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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1453-1459 
    ISSN: 1434-1948
    Keywords: Group-5 bent metallocene cation complexes ; (Butadiene)tantalocene cation ; (s-trans-η4-Butadiene)metal complex ; Ethene polymerization ; Metallocenes ; Homogeneous catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Butadiene)TaCp*Cl2 (6) was treated with CpNa to yield (η2-butadiene)TaCp*CpCl (7). Subsequent reaction with [Cp2ZrCH3+][CH3B(C6F5)3-] resulted in transfer of the chloride ligand from tantalum to zirconium with formation of the [(s-trans-η4-butadiene)TaCp*Cp]+ cation [8, with CH3B(C6F5)3- anion]. Complex 8 was characterized spectroscopically and by an X-ray crystal structure analysis. The group-5 [(s-trans-η4-C4H6)TaCp*Cp]+ bent metallocene cation complex 8 reacts with ketones (acetone, adamantanone) to yield the corresponding seven-membered 2-tantalatetrahydrooxepine cation complexes (9, 10). 1-Cyanoadamantane reacts with 8 to yield the 2-tantala-3,6-dihydro-2H-azepine cation system 11. Activation of 8 with methylalumoxane gives an active ethene polymerization catalyst.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-1948
    Keywords: “Constrained-geometry” Ziegler catalysts ; Cp/amido zirconium complex ; 6-Aminofulvene deprotonation ; Ethene polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 6-Amino-6-methylfulvene (4) is cleanly N-acylated by treatment with pivaloylchloride/triethylamine to give the fulvene (C5H4)=C(CH3)NHCOCMe3 (5c). Treatment of 4 with trimethylchlorosilane similarly yields the mono-N-silylated fulvene (C5H4)=C(CH3)NHSiMe3 (7). Both 5c and 7 are cleanly doubly deprotonated e.g. by treatment with LDA to give ligand systems [(C5H4)C(=CH2)NR]Li2 [8a (R = COCMe3) and 8b (R = SiMe3), respectively]. Their treatment with MCl4 · 2 THF (M = Ti, Zr) yield the spiro-metallocenes [(C5H4)C(=CH2)NR]2M (9, 10). Complex 10a (M = Zr, R = COCMe3) was characterized by X-ray diffraction. The reaction of 8a with (Et2N)2ZrCl2 in THF gives rise to the formation of [(C5H4)C(=CH2)NCOCMe3]Zr(NEt2)2 (11) (70 % isolated), and the reaction of 8b with (Et2N)2ZrCl2 yields [(C5H4)C(=CH2)NSiMe3]Zr(NEt2)2 (12) (76 % isolated). Treatment of complex 12 with an excess of methylalumoxane (MAO) in toluene solution results in the generation of an active homogeneous Ziegler catalyst for the polymerization of ethene. A comparison with the usually employed [(Me5C4)SiMe2NCMe3]ZrCl2/MAO “constrained-geometry” Ziegler catalyst system reveals a similar catalyst activity and performance of this novel type of a C1-bridged “constrained-geometry” catalyst as it is exemplified by the [(C5H4)C(=CH2)NSiMe3]ZrX2 (12)/MAO combination.
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