The influence of the coordination sphere of samarocenes on the synthesis of liquid crystalline polymethacrylates

(C5Me5)(2)Sm(THF)(2) (1) reacts with 1,3-Diisopropyl-3,5-dimethylimidazolin e-2-ylidene C(3)N(2)Me(2)iPr(2) (iPr-carben) with formation of (C5Me5)(2)Sm (iPr-carben) (3). The reaction of (C5Me4Et)(2)Sm(THF)(2) (2) with Al2Me6 in toluene yields [(C5Me4Et)(2)Sm(CH3)Al(CH3)(3)](2) (6) 3 and 6 were charact erized by single crystal X-ray structure analysis. Via living polymerizatio n of mesogenic methacrylates with the organosamarium complexes 1, 2, 3, (C5 Me5)(2)Sm(C3H5) (4), (C5Me5)(2)Sm(CH3) (THF) (5), 6, and (C5Me4Et)(2)SmCH-( SiMe3)(2) (7), liquid crystalline homo- and blockcopolymers were obtained w ith narrow molecular mass distribution indexes in high yield. Partial compe titive mechanisms are observed dependend of the structure of the catalyst a nd the polarity of the solvents.