Exploring Dinuclear Titanium Complexes in Titanium(III) Catalysis

The synthesis of one achiral and two chiral propylene‐bridged dititanocenes and their evaluation as catalysts in titanium(III) catalyzed ketone‐nitrile coupling reactions is reported. A reaction progress kinetics analysis of the cross‐coupling between acetophenone and benzyl cyanide reveals that, using a dinuclear titanocene catalyst, the order in catalyst is reduced from two to one in comparison to a mononuclear catalyst. Although the obtained coupling yields and enantioselectivities did not reach the results obtained with the latter, these examples constitute a proof‐of‐concept for the templated C‐C coupling through coordination of ketone and nitrile to the two tethered titanium centers of a dinuclear catalyst.