Chloro and Alkyl Rare-Earth Complexes Supported by ansa-Bis(amidinate) Ligands with a Rigid o‑Phenylene Linker. Ligand Steric Bulk: A Means of Stabilization or Destabilization?

ansa-Bis­(amidinate) ligands with a rigid o-phenylene linker, C6H4-1,2-{NC­(tBu)­N­(2,6-R2C6H3)­H}2 (R = Me (1), iPr (2)), were successfully employed for the synthesis of rare-earth chloro and alkyl species. The reaction of dilithium derivatives of 1 and 2 with LnCl3 (Ln = Y, Lu) afforded the monomeric bis­(amidinate) chloro lanthanide complexes [C6H4-1,2-{NC­(tBu)­N­(2,6-R2C6H3)}2]­Y­(THF)­(μ-Cl)2Li­(THF)2 (R = Me (3), iPr (5)) and [C6H4-1,2-{NC­(tBu)­N­(2,6-Me2C6H3)}2]­LuCl­(THF)2 (4). Bis­(amidinate) ligands in complexes 3 and 4 are coordinated to the metal atoms in a tetradentate fashion, while the bulkier ligand in 5 is tridentate. The alkane elimination reactions of 1 and 2 with equimolar amounts of (Me3SiCH2)3Ln­(THF)2 (Ln = Y, Lu) allowed us to obtain the monoalkyl complexes [C6H4-1,2-{NC­(tBu)­N­(2,6-R2C6H3)}2]­Ln­(CH2SiMe3)­(THF)n (Ln = Y, R = Me, n = 1 (6); Ln = Lu, R = Me, n = 1 (7); Ln = Y, R = iPr, n = 2 (8)). The kinetics of thermal decomposition of complexes 6–8 were measured, and for 6 the activation energy was obtained from the temperature dependence of the rate constants (Ea = 67.0 ± 1.3 kJ/mol). Complexes 6 and 7 turned out to be inert toward H2 and PhSiH3. Surprisingly, complex 8 was inert toward H2 and PhSiH3 but rapidly cleaved C–O bonds of DME. The reaction resulted in the formation of the methoxy complex {[C6H4-1,2-{NC­(tBu)­N­(2,6-iPr2C6H3)}2]­Y­(μ2-OMe)]}2(μ2-DME) (9) and methyl vinyl ether.