Perfluormethyl-Element-Liganden. XXXII. Reaktionen der Metallhydride π-C5H5(CO)3MH (M = Cr,Mo, W) mit Diphosphanen [Ph2−nYnP]2 (Y = I,CN, SiMe3; n = 2, 1, 0)

Perfluoromethyl Element Ligands. XXXII. Reactions of the Metal Hydrides π-C₅H₅(CO)₃MH (M = Cr, Mo, W) with Diphosphanes Ph_2?nY_nP]₂ (Y = I, CN, SiMe₃; n = 2, 1, 0) The reactions of π-C₅H₅(CO)₃MH (M = Cr, Mo, W) ( 1a – c ) with the symmetric diphosphanes (Ph₂P)₂, Ph(CN)P]₂, (CN)₂P]₂, and the cyclophosphane (PPh)₅, respectively, occur under cleavage of the P? P bond. The reactivity decreases in the series The tendency to form binuclear complexes reflects the basicity of the metallated phosphanes π-C₅H₅(CO)₃MPRR′ and increases in the order P(CN)₂ < P(CN)Ph ? P(Ph)H < PPh₂. Iodine containing diphosphanes Ph(I)P? P(I)Ph and P₂I₄] undergo redox reactions with 1a – c , yielding π-C₅H₅(CO)₃MI and unstable iodo-diphosphanes. No P? P bond cleavage occurs in the reaction of the silyl substituted diphosphanes Ph(SiMe₃)P]₂ and (Me₃Si)₂P]₂ with 1a – c , but P? Si bond fission is the preferred reaction giving π-C₅H₅(CO)₃MSiMe₃.