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)Pr(3))(2)}(2)(THF)(x)] (1-Ln; Ln = Sm, Eu, x = 3; Ln = Yb, x = 2), by the respective salt metathesis reactions of parent [LnI(2)(THF)(2)] with 2 equiv of [Na{P(Si(i)Pr(3))(2)}](n) in toluene. Complexes 1-Ln 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 1-Ln 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.