Bis(phosphinimino)methanide Rare Earth Amides: Synthesis, Structure, and Catalysis of Hydroamination/Cyclization, Hydrosilylation, and Sequential Hydroamination/Hydrosilylation
✍ Scribed by Marcus Rastätter; Agustino Zulys; Peter W. Roesky
- Publisher
- John Wiley and Sons
- Year
- 2007
- Tongue
- English
- Weight
- 309 KB
- Volume
- 13
- Category
- Article
- ISSN
- 0947-6539
No coin nor oath required. For personal study only.
✦ Synopsis
Abstract
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.