Rare-Earth-Metal-Promoted Hydroalumination

• Published in: European journal of inorganic chemistry 2013-07, Vol.2013 (19), p.3302-3306
• Main Authors: Schädle, Christoph, Anwander, Reiner
• Format: Article
• Language: English
• Subjects: Aluminum; Amides; Amido­alanes; Bimetals; Displays; Exchange; Hydride transfer reagents; Hydrides; Reagents; Transformations; Yttrium
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201300504

The capability of bis(trimethylsilyl)amidoalane to act as a hydride transfer reagent in organolanthanide chemistry was investigated by probing its reactivity toward alkylyttrium complexes. Reaction with Cp*2YMe(thf) led to the isolation of the bimetallic complex Cp*2Y(μ‐H)2Al(Me)[N(SiMe3)2] (Cp* = 1,2,3,4,5‐pentamethylcyclopentadiene), whereas reaction with [Cp*YMe2]3 gave MeAl[N(SiMe3)2]2 as the only isolable hydride transfer product. The dimeric complex [Cp*Y{N(SiMe3)2}(μ‐H)]2 represents one possible product of the aforementioned reaction that could be structurally characterized. The use of [YMe3]n as the alkylyttrium source led to the isolation of Y[N(SiMe3)2]3, which displays competition between amide and hydride transfer. Finally, the performance of Cp*2Y(μ‐H)2Al(Me)[N(SiMe3)2] and [YMe3]n in the hydroalumination of 1‐octene was tested, and these compounds represent the first rare‐earth metal catalysts for this transformation. YAH: Alkyl/hydrido exchange readily takes place when the yttrium methyl complexes (C5Me5)2YMe(thf), [(C5Me5)YMe2]3, and [YMe3]n are treated with the amidoalane HAl[N(SiMe3)2]2. The resulting heterobimetallics catalyze the addition of the amidoalane across 1‐octene, as shown for (C5Me5)2Y(μ‐H)2Al(Me)[N(SiMe3)2].