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

The reaction of the titanocene diphosphine {(η 5 -C 5 H 5 )[η 5 -C 5 Me 3 -1,2-(PPh 2 ) 2 ]TiCl 2 } (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.