Trimethylscandium

The hitherto unknown homoleptic tetramethyl­aluminate complex [Sc­(AlMe4)3] could be obtained by reacting the ate complex [Li3ScMe6(thf)1.2] with AlMe3 in the cold. It cocrystallizes with AlMe3 as [Sc­(AlMe4)3(Al2Me6)0.5] and decomposes at ambient temperature in n-pentane via multiple C–H bond activations to the mixed methyl/methylidene complex [Sc3(μ3-CH2)2(μ2-CH3)3­(AlMe4)2(AlMe3)2]. Donor-induced methylaluminate cleavage of [Sc­(AlMe4)3(Al2Me6)0.5] produced [ScMe3]n in good yield, which could be derivatized with trimethyltriazacyclononane (Me3TACN) to form the structurally characterizable [(Me3TACN)­ScMe3]. Additionally, half-sandwich complex [Cp*Sc­(AlMe4)2] and sandwich complex [Cp*2Sc­(AlMe4)] were accessible by salt metathesis reactions from [Sc­(AlMe4)3(Al2Me6)0.5] and KCp* (Cp* = C5Me5). 45Sc NMR spectroscopy was applied as a significant probe to evidence the existence of [ScMe3]n. Compounds [(Me3TACN)­ScMe3] (+624.6 ppm) and [ScMe3(thf)x] (+601.7 ppm) gave large 45Sc NMR shifts, revealing the strong deshielding effect of the σ-bonded alkyl ligands on the scandium nuclei. Ultimately, cationized [Sc­(AlMe4)3­(Al2Me6)0.5] was employed in isoprene polymerization, leading to polymers in high yields (>95%) and with high (>90%) cis-1,4-polyisoprene content.