Synthesis, Structural Characterization, and Theoretical Investigation of Compounds Containing an Al−O−M−O−Al (M = Ti, Zr) Core<sup>†</sup> MandalSwadhin K. GurubasavarajPrabhuodeyara M. RoeskyHerbert W. OswaldRainer B. MagullJörg RingeArne 2007 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(NMe<sub>2</sub>)<sub>2</sub>(μ-O)Al(Me)L [L = CH{N(Ar)(CMe)}<sub>2</sub>, Ar = 2,6-<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>; M = Ti (<b>7</b>), Zr (<b>8</b>)] was accomplished by reacting the monometallic hydroxide precursor L(Me)Al(OH) (<b>1</b>) with Ti(NMe<sub>2</sub>)<sub>4</sub> or Zr(NMe<sub>2</sub>)<sub>4</sub> under elimination of Me<sub>2</sub>NH in good yield. The crystal structural data confirm the trimetallic Al−O−M−O−Al core in both <b>7</b> and <b>8</b>. 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)Cp<sub>2</sub> (M = Ti, Zr) which could be attributed to the relatively lower stability of the supposed cationic intermediate as revealed by DFT calculations.