Wj. Evans et al., SYNTHESIS, STRUCTURE, AND REACTIVITY OF CYCLOPENTADIENYL-FREE TRIMETHYLSILYLMETHYL YTTRIUM DI-TERT-BUTYLPHENOXIDE COMPLEXES, Journal of organometallic chemistry, 569(1-2), 1998, pp. 89-97
The chemistry of yttrium with the trimethylsilylmethyl/2,6-di-tert-but
yl-phenoxide ligand combination has been examined. The anionic dialkyl
-diaryloxide complexes, {(Me3SiCH2)(2)Ln((OC6H3Bu2)-Bu-t-2,6)(2)}(-) (
Ln = Y, Lu), were prepared and their reactivity and that of the neutra
l dialkyl-aryloxide complex (Me3SiCH2)(2)Y((OC6H3Bu2)-Bu-t-2,6)(THF)(2
), 1, has been studied and compared with cyclopentadienyl-containing o
rganolanthanide complexes. {(Me3SiCH2)(2)Y((OC6H3Bu2)-Bu-t-2,6)(2)} {[
(THF)(3)Li](2)Cl}, 2, was prepared from the reaction of YCl3 with two
equivalents of LiCH2SiMe3 and two equivalents of (LiOC6H3Bu2)-Bu-t-2,6
and crystallized with an unusual cation which can be viewed as a LiCl
adduct of [Li(THF)(x)](+). (2)Lu((OC6H3Bu2)-Bu-t-2,6)(2)][Li(THF)(4)]
(THF)(2) 3, was prepared analogously and crystallized with a conventio
nal cation. Both 2 and 3 have distorted tetrahedral coordination geome
tries around the metals. Ring-opening polymerization of epsilon-caprol
actone was observed for 1-3, but only complex 1 was found to polymeriz
e ethylene. NMR and mass spectroscopic analyses show that the more rea
ctive complex 1 also exhibits metallation reactivity with pyridine, to
luene, phenylacetylene, CH3CN, Me2CHCN, PhCN, and PhCH2CN and insertio
n chemistry with Me3CNC, CO, CO2, PhNCO, and PhNCS. However, isolation
of the organometallic products has been difficult due to the complexi
ty of the reaction mixtures. (C) 1998 Elsevier Science S.A. All rights
reserved.