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

The reaction of the titanocene diphosphine {(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)[η<sup>5</sup>-C<sub>5</sub>Me<sub>3</sub>-1,2-(PPh<sub>2</sub>)<sub>2</sub>]TiCl<sub>2</sub>} (TiPHOS; <b>1</b>) with [Rh(COD)<sub>2</sub>](OTf) led to the new early−late heterobimetallic complex [(TiPHOS)Rh(COD)](OTf) (<b>2</b>), 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 <b>2</b> has been tested in parallel with the monometallic complex [(<i>o</i>-dppbe)Rh(COD)](OTf) (<b>3</b>) and has proved to be a very effective catalyst for the hydrosilylation of aromatic ketones.