Synthesis and Characterization of Solvated Lanthanide(II) Bis(triisopropylsilyl)phosphide Complexes

Lanthanide (Ln) silylamide chemistry is well-developed, but the corresponding silylphosphide chemistry is immature; there are only ten structurally characterized examples of Ln(II) bis(trimethylsilyl)phosphide complexes to date and no reported derivatives with bulkier R-groups. Here, we report the synthesis of the first f-block bis(triisopropylsilyl)phosphide complexes, [Ln{P(Si^<i>i</i>Pr₃)₂}₂(THF)_<i>x</i>] (<b>1-Ln</b>; Ln = Sm, Eu, <i>x</i> = 3; Ln = Yb, <i>x</i> = 2), by the respective salt metathesis reactions of parent [LnI₂(THF)₂] with 2 equiv of [Na{P(Si^<i>i</i>Pr₃)₂}]_<i>n</i> in toluene. Complexes <b>1-Ln</b> were characterized by a combination of NMR, EPR, ATR-IR, electronic absorption and emission spectroscopies, elemental analysis, SQUID magnetometry, and single crystal X-ray diffraction. These data contrast with those obtained for related Ln(II) bis(trimethylsilyl)phosphide complexes due to the bulkier ligands in <b>1-Ln</b> and also with Ln(II) bis(triisopropylsilyl)amide complexes due to a combination of longer Ln-P vs. Ln-N bonds and the softer nature of P- vs. N-donor ligands.