Cationic Rare-Earth Metal Trimethylsilylmethyl Complexes Supported by THF and 12-Crown-4 Ligands: Synthesis and Structural Characterization

To expand the limited range of rare-earth metal cationic alkyl complexes known, a series of mono- and dicationic
trimethylsilylmethyl complexes supported by THF and 12-crown-4 ligands with [BPh4]-, [BPh3(CH2SiMe3)]-, [B(C6F5)4]-,
[B(C6F5)3(CH2SiMe3)]-, and [Al(CH2SiMe3)4]- anions were prepared from corresponding neutral precursors
[Ln(CH2SiMe3)3Ln] (Ln = Sc, Y, Lu; L = THF, n = 2 or 3; L = 12-crown-4, n = 1) as solvent-separated ion pairs.
The syntheses of the monocationic derivatives [Ln(CH2SiMe3)2(12-crown-4)n(THF)m]+[A]- are all high yielding and
proceed rapidly in THF solution at room temperature. A “one pot” procedure using the neutral species directly for
the syntheses of a number of lutetium and yttrium dicationic derivatives [Ln(CH2SiMe3)(12-crown-4)n(THF)m]2+[A]-2
with a variety of different anions, a class of compounds previously limited to just a few examples, is presented.
When BPh3 is used to generate the ion triple, the presence of 12-crown-4 is required for complete conversion.
Addition of a second equiv of 12-crown-4 and a third equiv of [NMe2PhH]+[B(C6F5)4]- abstracts a third alkyl group
from [Ln(CH2SiMe3)(12-crown-4)2(THF)x]2+[B(C6F5)4]-2 (Ln = Y, Lu). X-ray crystallography and variable-temperature
(VT) NMR spectroscopy reveal a structural diversity within the known series of neutral 12-crown-4 supported tris(trimethylsilylmethyl) complexes [Ln(CH2SiMe3)3(12-crown-4)] (Ln = Sc, Y, Sm, Gd−Lu) in the solid and solution
states. The X-ray structure of [Sc(CH2SiMe3)3(12-crown-4)] exhibits incomplete 12-crown-4 coordination. VT NMR
spectroscopy indicates fluxional 12-crown-4 coordination on the NMR time scale. X-ray crystallography of only the
second structurally characterized dicationic rare-earth metal alkyl complex [Y(CH2SiMe3)(12-crown-4)(THF)3]2+[BPh4]-2
shows exocyclic 12-crown-4 coordination at the 8-coordinate metal center with well separated counteranions. 11B
and 19F NMR spectroscopy of all mono- and dicationic rare-earth metal complexes reported demonstrate that the
anions are symmetrical and noncoordinating on the NMR time scale. A series of trends within the 1H and 13C{1H}
NMR resonances arising from the Ln-CH2 groups and, in the case of yttrium, the 1JYC coupling constants at the
Y−CH2 group and the 89Y chemical shift values are discussed.