The coordination of a 2,2′‐bipyridyl derivative to a (C5Me5)RuII fragment provides both a facile route to unprecedented dicationic (allyl)RuIV complexes (see picture) and new highly efficient catalysts for the regioselective allylic substitution from unsymmetrical allylic carbonates.

6 ] disclosed an (endo-trans-MeCHCHCH 2 ) allylic ligand. The structural information obtained from the study of Cp*(allyl)Ru(IV) complexes indicated that electronic effects at the coordinated allylic ligand likely account for the better regioselectivity obtained from cinnamyl chloride as compared to aliphatic allylic chlorides.