Abstract
The equimolar reaction of [(C5Me5)LnMe2]3 (Ln = Y, Lu) with (DippForm)AlMe2 gave the ligand-rearranged complexes (C5Me5)Ln(AlMe4)(DippForm) in quantitative yields. The half-sandwich complexes were fully characterized including X-ray structure analyses. Donor solvent (THF)-induced alkylaluminate cleavage of (C5Me5)Lu(AlMe4)(DippForm) gave complex [(C5Me5)LuMe(DippForm)(thf)] exclusively, as evidenced by 1H‒13C HSQC NMR spectroscopy. Treatment of polymeric [LuMe3]n with formamidine DippFormH produced a mixture of two compounds, namely, the bis(formamidinate) complex (DippForm)2LuMe and the methyl methylidene complex [{(DippForm)Lu(μ2-Me)}3(μ3-Me)(μ3-CH2)]. While monomeric (DippForm)2LuMe revealed a very short Lu–C terminal methyl bond lengths of 2.314(3) Å in the solid state, the structure of the trimetallic methylidene complex could be assigned unambiguously on the basis of a 1H‒13C HSQC NMR spectrum. Preliminary studies on the performance of complex (C5Me5)Y(AlMe4)(DippForm) in isoprene polymerization revealed that upon activation with borate co-catalysts [Ph3C][B(C6F5)4] and [PhNMe2H][B(C6F5)4] highly active catalyst systems are obtained, producing polyisoprenes with dominant 3,4-units (57% and 58%).
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