As previously shown for lutetium and yttrium, 1,2,3,4,5-pentamethylcyclopentadienyl (C5Me5 = Cp*)-bearing rare-earth metal dimethyl half-sandwich complexes [Cp*LnMe2]3 are now also accessible for holmium, dysprosium, and terbium via tetramethylaluminato cleavage of [Cp*Ln(AlMe4)2] with diethyl ether (Ho, Dy) and tert-butyl methyl ether (TBME) (Tb). C-H-bond activation and ligand redistribution reactions are observed in case of terbium and are dominant for the next larger-sized gadolinium, as evidenced by the formation of mixed methyl/methylidene clusters [(Cp*Ln)5(CH2)(Me)8] and metallocene dimers [Cp*2Ln(AlMe4)]2 (Ln = Tb, Gd). Applying TBME as a "cleaving" reagent can result in both TBME deprotonation and ether cleavage, as shown for the formation of the 24-membered macrocycle [(Cp*Gd)2(Me)(CH2OtBu)2(AlMe4)]4 or monolanthanum complex [Cp*La(AlMe4){Me3Al(CH2)OtBu}] and monoyttrium complex [Cp*Y(AlMe4)(Me3AlOtBu)], respectively. Complexes [Cp*Ln(AlMe4)2] (Ln = Ho, Dy, Tb, Gd) and [Cp*LnMe2]3 (Ln = Ho, Dy) are applied in isoprene and 1,3-butadiene polymerization, upon activation with borates [Ph3C][B(C6F5)4] and [PhNHMe2][B(C6F5)4], as well as borane B(C6F5)3. The trans-directing effect of AlMe3 in the binary systems [Cp*Ln(AlMe4)2]/borate is revealed and further corroborated by the fabrication of high-cis-1,4 polybutadiene (97%) with "aluminum-free" [Cp*DyMe2]3/[Ph3C][B(C6F5)4]. The formation of multimetallic active species is supported by the polymerization activity of pre-isolated cluster [(Cp*Ho)3Me4(CH2)(thf)2].
Keywords: 1,3-diene polymerization; C-H-bond activation; cluster; lanthanides; methyl.