Preparation of Cp-Functionalized N-Heterocyclic Carbene Complexes of Ruthenium. Resolution of Chiral Complexes and Catalytic Studies

A series of piano-stool ruthenium(II) complexes bearing bidentate cyclopentadienyl-functionalized N-heterocyclic carbene ligands Ru(Cp-X-NHC)(CO)I [Cp = tetramethylcyclopentadienyl (Cp*) and tetrabenzylcyclopentadienyl (Cp-Bz)] have been prepared by the diastereoselective reaction of the imidazolium Cp-X-NHC proligands with [Ru-3(CO)(12)]. The new complexes have been characterized by spectroscopic techniques and X-ray diffraction methods. The enantiopure complexes have been separated by preparative thin-layer chromatography of the diastereomeric mixtures resulting from the reaction of the Ru(Cp-X-NHC)(CO)I compounds with an auxiliary chiral amine. Ru(Cp*-NHC)(CO)I is an efficient catalyst for the isomerization of allylic alcohols both in water and in THF.