X-ray, ¹³C NMR, and DFT Studies on a Ruthenium(IV) Allyl Complex. Explanation for the Observed Control of Regioselectivity in Allylic Alkylation Chemistry

X-ray, 13 C NMR, and DFT studies on the cationic Ru(IV) allyl complex Ru(Cp*)Cl(CH 3 CN)(η 3 -PhCHCHCH 2 ), as a PF 6 salt, have revealed a marked asymmetry in the bonding of the allyl ligand, which can be interpreted as arising from differences in π-bonding from the metal center to the two terminal allyl carbons. This asymmetry in the bonding is offered as an explanation for the observed control of regioselectivity in the Ru-catalyzed allylic alkylation reaction.