Transition metal–carbon bonds. Part XVII. Some allylic complexes of iridium(III)

Abstract

Treatment of complexes of type mer-[IrCl₃P₃](P = PEt₃, PMe₂Ph, or PEt₂Ph) with 2-methylallylmagnesium chloride gives complexes of the type [IrCl₂(π-2-methylallyl)P₂]. Similarly, treatment of mer-[IrCl₃(PEt₃)₃] with allylmagnesium chloride gives [IrCl₂(π-allyl)(PEt₃)₂] but mer-[IrCl₃(PMe₂Ph)₃] with allylmagnesium chloride gives [IrCl₂(σ-allyl)(PMe₂Ph)₃]. This σ-allyl complex with KOH in methanol gave [IrCl₂(π-allyl)(PMe₂Ph)₂]. Treatment of [IrCl₂(π-2-methylallyl)(PMe₂Ph)₂] with dilute hydrochloric acid gives a bridged chloro-complex, [Ir₂Cl₆(PMe₂Ph)₄]. Treatment of [IrCl₂(π-2-methylallyl)(PMe₂Ph)₂] with carbon monoxide gives the σ-2-methylallyl complex [IrCl₂(C₄H₇)(CO)(PMe₂Ph)₂]. Treatment of mer-[IrCl₃(PEt₃)₃] with 2-methylallylmagnesium chloride gave [Ir(π-2-methylallyl)₂(PEt₃)₂]⁺ isolated as its tetraphenylborate salt.