Synthesis and Complexation of the Metalloligand {(η5-C5H5)[η5-C5Me3-1,2-(PPh2)2]TiCl2} (TiPHOS): The First Example of a 1,2-Bis(diphenylphosphanyl)titanocene Derivative

The reaction of lithium 1,2-bis(diphenylphosphanyl)trimethylcyclopentadienide (1) with CpTiCl3 leads to the formation of the titanocene diphosphane {(η5-C5H5)[η5-C5Me3-1,2-(PPh2)2]TiCl2} (TiPHOS, 2). This metalloligand reacts readily with (NBD)Cr(CO)4 and W(CO)5(THF) to give, in both cases, the bimetallic chelate complexes (TiPHOS)Cr(CO)4 (3) and (TiPHOS)W(CO)4 (4). The structure of 4 has been determined by X-ray diffraction. The synthesis of a new early-late heterobimetallic complex (TiPHOS)Rh(CO)Cl (5) is reported.