Abstract
AbstractHalf‐sandwich rare‐earth metal tetramethylaluminate complexes [Ln(η5‐C5Me4SiMe3){(μ‐Me)2(AlMe2)}2] (Ln = Y, La, Nd, Sm, Gd, Lu) were obtained by reaction of the neutral homoleptic tetramethylaluminate complex [Ln{(μ‐Me)2(AlMe2)}3] with tetramethyl(trimethylsilyl)cyclopentadiene, (C5Me4H)SiMe3. Protonolysis reaction of the neutral mono(cyclopentadienyl) complexes with the Brønsted acid [NEt3H]+[BPh4]– in thf led to the formation of the monocationic methyl complexes [Ln(η5‐C5Me4SiMe3)Me(thf)3]+[BPh4]– (Ln = Y, La, Nd, Sm, Lu). Single‐crystal X‐ray diffraction study on the Y, Sm, and Lu derivatives showed a four‐legged piano‐stool configuration. Upon activation with [Ph3C]+[B(C6F5)4]–, the neutral half‐sandwich tetramethylaluminate complex [La(η5‐C5Me4SiMe3){(μ‐Me)2(AlMe2)}2] catalyzed the polymerization of butadiene in the presence of [AliBu3] to give trans‐1,4‐polybutadiene with narrow polydispersities (Mn/Mw = 1.05–1.09).(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
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