Syntheses of Dianionic α-Iminopyridine Rare-Earth Metal Complexes and Their Catalytic Acitivities toward Dehydrogenative Coupling of Amines with Hydrosilanes.

Reactions of [(MeSi)N]RE(μ-Cl)Li(THF) with aminomethylene-substituted pyridine 2-[O(CHCH)NCHCHNCH]CHN () gave the dianionic α-iminopyridine rare-earth metal amido complexes {μ-η:σ:κ:κ-2-[O(CHCH)NCHCHNCH]CHN}RE[N(SiMe)] (RE = Y(), La(), Pr(), Nd(), Sm(), Dy(), Er(), and Lu ()). However, reaction of [(MeSi)N]Y(μ-Cl)Li(THF) with pyridin-2-ylmethyl-substituted amines such as 2-(RNHCH)CHN (R = Bu () and 2,6-PrPh ()) or benzyl-substituted amine O(CHCH)NCHCHNHCHCH () afforded the corresponding yttrium complexes containing monoanionic ligands [2-(RNCH)CHN]YN(SiMe) (R = Bu () and 2,6-PrPh ()) or [O(CHCH)NCHCHNCHCH][(MeSi)N)]Y(μ-Cl)(μ-η-O(CHCH)NCHCHNCHCH)Li(THF) (). Dianionic α-iminopyridine rare-earth metal amido complexes showed high catalytic activities for the dehydrogenation coupling reaction of hydrosilanes and amines providing a variety of silylamines in high yields.