Reactions of primary silanes with hydridotetrakis(trimethylphosphine)iridium and chlorotetrakis(trimethylphosphine)iridium.

摘要

HIr(PMe₃)₄ reacts slowly at room temperature with all primary silanes SiRH₃ (R = Ph, p-tolyl, n-hexyl, n-pentyl, and t-Bu) examined. The major product in each case is the facial complex H ₂Ir(PMe₃)₃(SiH₂R) obtained in 70–95% yield. However varying amounts of other minor products, such as the meridional isomers, cyclometallated products and iridium-silicon rings, can be obtained by varying the reaction conditions and the silane used. The primary silane complexes appear to be less thermodynamically stable than the complexes obtained from secondary or tertiary silanes.; Reactions of ClIr(PMe₃)₃ with primary silanes are more complex. Reactions can be run neat with excess silane, in benzene, in toluene, or in DMSO. The products vary with the solvent used. The major product is the ionic compound [HIr(PMe₃)₄Si(R)H₂] +Cl−. Silane oligomers were among the side products formed in this reaction if there was excess silane. The principal product is not stable in air or most ionic solvents and forms both ionic and molecular degradation products.