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  • Title: Synthesis, structural characterization, and theoretical investigation of compounds containing an Al-O-M-O-Al (M=Ti, Zr) core.
    Author: Mandal SK, Gurubasavaraj PM, Roesky HW, Oswald RB, Magull J, Ringe A.
    Journal: Inorg Chem; 2007 Sep 03; 46(18):7594-600. PubMed ID: 17685512.
    Abstract:
    We report a facile route to the first molecular compounds with the Al-O-M-O-Al (M=Ti, Zr) structural motif. Synthesis of L(Me)Al(mu-O)M(NMe2)2(mu-O)Al(Me)L [L=CH{N(Ar)(CMe)}2, Ar=2,6-iPr2C6H3; M=Ti (7), Zr (8)] was accomplished by reacting the monometallic hydroxide precursor L(Me)Al(OH) (1) with Ti(NMe2)4 or Zr(NMe2)4 under elimination of Me2NH in good yield. The crystal structural data confirm the trimetallic Al-O-M-O-Al core in both 7 and 8. Preliminary investigation on catalytic activity of these complexes reveals low activity of these complexes in ethylene polymerization as compared to the related oxygen-bridged metallocene-based heterobimetallic complexes L(Me)Al(mu-O)M(Me)Cp2 (M=Ti, Zr) which could be attributed to the relatively lower stability of the supposed cationic intermediate as revealed by DFT calculations.
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