[TiPHOS(Rh)]⁺:  A Fortuitous Coordination Mode and an Effective Hydrosilylation Bimetallic Catalyst

The reaction of the titanocene diphosphine {(η⁵-C₅H₅)[η⁵-C₅Me₃-1,2-(PPh₂)₂]TiCl₂} (TiPHOS; 1) with [Rh(COD)₂](OTf) led to the new early−late heterobimetallic complex [(TiPHOS)Rh(COD)](OTf) (2), whose structure has been determined by X-ray diffraction analysis and by dynamic NMR studies. A weak bonding interaction between one of the two chloride atoms of the TiPHOS ligand and the rhodium center has been observed. The bimetallic complex 2 has been tested in parallel with the monometallic complex [(o-dppbe)Rh(COD)](OTf) (3) and has proved to be a very effective catalyst for the hydrosilylation of aromatic ketones.