Synthesis and Characterization of Yttrium Methanediide Silanide Complexes

The salt metathesis reactions of the yttrium methanediide iodide complex [Y(BIPM)(I)(THF)₂] (BIPM = {C(PPh₂NSiMe₃)₂}) with the group 1 silanide ligand-transfer reagents MSiR₃ (M = Na, R₃ = Bu₂Me or Bu₃; M = K, R₃ = (SiMe₃)₃) gave the yttrium methanediide silanide complexes [Y(BIPM)(SiBu₂Me)(THF)] (1), [Y(BIPM)(SiBu₃)(THF)] (2), and [Y(BIPM){Si(SiMe₃)₃}(THF)] (3). Complexes 1-3 provide rare examples of structurally authenticated rare earth metal-silicon bonds and were characterized by single-crystal X-ray diffraction, multinuclear NMR and ATR-IR spectroscopies, and elemental analysis. Density functional theory calculations were performed on 1-3 to probe their electronic structures further, revealing predominantly ionic Y-Si bonding. The computed Y-Si bonds show lower covalency than Y═C bonds, which are in turn best represented by Y⁺-C^- dipolar forms due to the strong σ-donor properties of the silanide ligands investigated; these observations are in accord with experimentally obtained ¹³C{¹H} and ²⁹Si{¹H} NMR data for 1-3 and related Y(III) BIPM alkyl complexes in the literature. Preliminary reactivity studies were performed, with complex 1 treated separately with benzophenone, azobenzene, and N,N'-dicyclohexyl-carbodiimide. ²⁹Si{¹H} and ³¹P{¹H} NMR spectra of these reaction mixtures indicated that 1,2-migratory insertion of the unsaturated substrate into the Y-Si bond is favored, while for the latter substrate, a [2 + 2]-cycloaddition reaction also occurs at the Y═C bond to afford [Y{C(PPh₂NSiMe₃)₂[C(NCy)₂]-κ⁴C,N,N',N'}{C(NCy)₂(SiBu₂Me)-κ²N,N'}] (4); these reactivity profiles complement and contrast with those of Y(III) BIPM alkyl complexes.