Unprecedented double nucleophilic addition of a hydride at a central carbon of an eta3-allyl ligand.
Treatment of eta(3)-allyl compound [Cp(2)Mo(eta(3)-C(3)H(5))](+)(1; Cp =eta(5)-C(5)H(5)) with MH (M = Li, Na) resulted in reduction of the allyl ligand to give propane. Deuterium-labeling studies were used to trace the origins and fates of the hydrogen atoms. The mechanism is discussed in light of the HSAB principle. The studies showed that the formation of propane can be explained by 1,2-hydrogen migration from the central to the terminal carbon of the allyl ligand, and the subsequent double nucleophilic addition of the hydride at the central carbon.
Minato
Makoto
M
Department of Materials Chemistry, Graduate School of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, Japan 240-8501. minato@ynu.ac.jp.
Sekimizu
Ryoko
R
Uchida
Daisuke
D
Ito
Takashi
T