摘要:
The reaction of halflanthanidocene aryloxides Cp(R')Ln(OArtBu,R)(2) (Ln = Y, La, Lu; Cp-R' = C5Me5, C4Me4H; R = H, Me) and half-lanthanidocene alkoxides [(C5Me5)Ln(OCH2CMe3)(2)](2) (Ln = Y, Lu) with trimethylaluminum (TMA) was investigated. Monomeric Cp(R')Ln(OArtBu,R)(2), derived from the ortho-tBu-substituted OC(6)H(2)tBu(2)-2,6-R-4 (R = H, Me) ligands, form mono(tetramethylaluminate) complexes Cp(R')Ln(OArtBu,R)(AlMe4) for the smaller lanthanide metal centers yttrium and lutetium. Such an [aryloxide] -> [aluminate] ligand exchange was not observed at the larger lanthanum metal center. The mobility of the tetramethylaluminate ligands of complexes Cp(R')Ln(OArtBu,R)(AlMe4) (Ln = Y, Lu) was examined by variable-temperature (VT) H-1 NMR spectroscopy, revealing two signals for bridging and terminal methyl groups at lower temperatures. The treatment of complexes Cp(R')Ln(OArtBu,R)(AlMe4) with donor solvent d(8)-THF gave Cp(R')Ln(OArtBu,R)(Me)(d(8)-THF)(2) (Ln = Y, Lu) with terminal methyl groups, according to a donor-induced aluminate cleavage reaction. Dimeric [(C5Me5)Ln(OCH2CMe3)(2)](2) (Ln = Y, Lu) was synthesized from (C5Me5)Ln(NiPr2)(2)(THF) and reacted with two equivalents of TMA per Ln center to yield monomeric bis(TMA) adduct complexes (C5Me5)Ln(OCH2CMe3)(2)(AlMe3)(2) (Ln = Y, Lu). VT NMR spectroscopic studies confirmed a high mobility of the Ln(mu-OCH2CMe3)(mu-Me)AlMe2 moieties at an ambient temperature. Both bis(TMA) adduct complexes were characterized by X-ray structure analysis. (c) 2006 Elsevier B.V. All rights reserved.