Directed Lithiation of Pentadienylsilanes

Deprotonation of dimethyl­(pyrrolidylmethyl)­silylpentadiene (5) and bis­(2-methoxyethyl)­aminomethyl­(dimethyl)­silylpentadiene (7) with nBuLi/tmeda and nBuLi, respectively, results in their corresponding lithium complexes, 6 and 8. The lithium cation in 6 is coordinated by an η1-pentadienyl ligand via the α-carbon and by the pendant pyrrolidyl group. The lithium cation in 8 is η2 coordinated by the pentadienyl α- and β-carbons and by the bis­(methoxyethyl)­amino group. The structure of 6 is retained in benzene solution, but in thf the tmeda coligand is displaced by the solvent. A 3.5:1 mixture of the W- and S-conformations of the pentadienyl carbons was observed for 8 in benzene. DFT calculations of NBO charges for the pentadienyl carbons in 6 and 8 show that lithium polarizes the electron density toward the α-carbon, although a series of electrophile quenching reactions with 6 show that regioselectivity does not depend on the electronic structure of the pentadienyl carbanion.