ic701063v_si_003.pdf (52.44 kB)

Synthesis, Structural Characterization, and Theoretical Investigation of Compounds Containing an Al−O−M−O−Al (M = Ti, Zr) Core

Download (52.44 kB)
journal contribution
posted on 03.09.2007 by Swadhin K. Mandal, Prabhuodeyara M. Gurubasavaraj, Herbert W. Roesky, Rainer B. Oswald, Jörg Magull, Arne Ringe
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(μ-O)M(NMe2)2(μ-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(μ-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.

History

Exports