We report the extension of the series of {BIPM
TMSH}
− (BIPM
R = C{PPh
2NR}
2, TMS = trimethylsilyl) derived rare earth methanides by the preparation of [Ln(BIPM
TMSH)(I)
2(THF)] (Ln = Nd, Gd, Tb),
1a–c,
[...] Read more.
We report the extension of the series of {BIPM
TMSH}
− (BIPM
R = C{PPh
2NR}
2, TMS = trimethylsilyl) derived rare earth methanides by the preparation of [Ln(BIPM
TMSH)(I)
2(THF)] (Ln = Nd, Gd, Tb),
1a–c, in 34–50% crystalline yields via
the reaction of [Ln(I)
3(THF)
3.5] with [Cs(BIPM
TMSH)]. Similarly, we have extended the range of {BIPM
MesH}
− (Mes = 2,4,6-trimethylphenyl) derived rare earth methanides with the preparation of [Gd(BIPM
MesH)(I)
2(THF)
2],
3, (49%) and [Yb(BIPM
MesH)(I)
2(THF)],
4,
(26%), via the reaction of [Ln(I)
3(THF)
3.5] with [{K(BIPM
MesH)}
2]. Attempts to prepare dysprosium and erbium analogues of
3 or
4 were not successful, with the ion pair species [Ln(BIPM
MesH)
2][BIPM
MesH] (Ln = Dy, Er),
5a–b, isolated in 31–39% yield. The TMEDA (
N',
N',
N",
N"-tetramethylethylenediamine) adducts [Ln(BIPM
MesH)(I)
2(TMEDA)] (Ln = La, Gd),
6a–b, were prepared in quantitative yield via the dissolution of [La(BIPM
MesH)(I)
2(THF)] or
3 in a TMEDA/THF solution. The reactions of [Ln(BIPM
MesH)(I)
2(THF)] [Ln = La, Ce, Pr, and Gd (
3)] or
6a–b with a selection of bases did not afford [La(BIPM
Mes)(I)(S)
n] (S = solvent) as predicted, but instead led to the isolation of the heteroleptic complexes [Ln(BIPM
Mes)(BIPM
MesH)] (Ln = La, Ce, Pr and Gd),
7a–
d, in low yields due to ligand scrambling.
Full article
