Der Einfluß der Koordinationssphäre von Samarocenen auf die Synthese von flüssigkristallinen Polymethacrylaten

The Influence of the Coordination Sphere of Samarocenes on the Synthesis of Liquid Crystalline Polymethacrylates (C₅Me₅)₂Sm(THF)₂ ( 1 ) reacts with 1,3‐Diisopropyl‐4,5‐dimethylimidazoline‐2‐ylidene C₃N₂Me₂iPr₂ (iPr‐carben) with formation of (C₅Me₅)₂Sm(iPr‐carben) ( 3 ). The reaction of (C₅Me₄Et)₂Sm(THF)₂ ( 2 ) with Al₂Me₆ in toluene yields [(C₅Me₄Et)₂Sm(CH₃)Al(CH₃)₃]₂ ( 6 ). 3 and 6 were characterized by single crystal X‐ray structure analysis. Via living polymerization of mesogenic methacrylates with the organosamarium complexes 1 , 2 , 3 , (C₅Me₅)₂Sm(C₃H₅) ( 4 ), (C₅Me₅)₂Sm(CH₃)(THF) ( 5 ), 6 , and (C₅Me₄Et)₂SmCH(SiMe₃)₂ ( 7 ), liquid crystalline homo‐ and blockcopolymers were obtained with narrow molecular mass distribution indexes in high yield. Partial competitive mechanisms are observed dependend of the structure of the catalyst and the polarity of the solvents.     

Neue ternäre Selenide der Lanthanide durch Reduktion der Sesquiselenide

New Ternary Selenides of Lanthanoides by Reduction of Sesquiselenides The compounds MLn₂Se₃ (M = Na; Ln = La? Sm) and MLn₈Se₁₂ (M = Na, Ca; Ln = La? Sm) were prepared by reduction of the corresponding lanthanide sesquiselenides with sodium and calcium, respectively, for the first time. Further-more MLa₈Se₁₂ (M = Sr, Eu) could be obtained in an analogous way. All compounds were characterized by chemical analysis and X-ray powder diffraction. The electronic structures of these compounds were investigated by band structure calculations and magnetic measurements.