Bis(phosphinimino)methanide Rare Earth Amides: Synthesis, Structure, and Catalysis of Hydroamination/Cyclization, Hydrosilylation, and Sequential Hydroamination/Hydrosilylation

A series of yttrium and lanthanide amido complexes [Ln{N(SiHMe 2 ) 2 } 2 {CH(PPh 2 NSiMe 3 ) 2 }] (Ln=Y, La, Sm, Ho, Lu) were synthesized by three different pathways. The title compounds can be obtained either from [Ln{N(SiHMe 2 ) 2 } 3 (thf) 2 ] and [CH 2 (PPh 2 NSiMe 3 ) 2 ] or from KN(SiHMe 2 ) 2 and [Ln{CH(PPh 2 NSiMe 3 ) 2 }Cl 2 ] 2 , while in a third approach the lanthanum compound was synthesized in a one‐pot reaction starting from K{CH(PPh 2 NSiMe 3 ) 2 }, LaCl 3 , and KN(SiHMe 2 ) 2 . All the complexes have been characterized by single‐crystal X‐ray diffraction. The new complexes, [Ln{N(SiHMe 2 ) 2 } 2 {CH(PPh 2 NSiMe 3 ) 2 }], were used as catalysts for hydroamination/cyclization and hydrosilylation reactions. A clear dependence of the reaction rate on the ionic radius of the center metal was observed, showing the lanthanum compound to be the most active one in both reactions. Furthermore, a combination of both reactions—a sequential hydroamination/hydrosilylation reaction—was also investigated.