Coordination Chemistry of {[Zr]−Cl−[Zr]}+ Complexes

Abstract

Treatment of the tris(cyclopentadienyl) cation (1+) with zirconocene dichloride 2 gave, in almost quantitative yield, the 1:1 adduct 7+, which was isolated with [(CH3)B(C6F5)3]− as the counterion. Reaction of 1+ with the organometallic ligand Cp3ZrCl afforded the 1:1 adduct 8+, again isolated with [(CH3)B(C6F5)3]−. The X-ray analysis revealed that 7+ displays a strongly bent Zr−Cl−Zr coordination mode, in contrast to 8+, which has a tendency to linear coordination. A theoretical analysis suggests that a subtle balance between steric and electronic factors determines the geometries in such organometallic adducts.