Notes. Some rhodium(III)–dihalogenophosphine complexes

Abstract

Reaction between trans-[RhBr(CO)(PEt₃)₂] and PF₂Br at 190 K gives [RhBr(CO)(PEt₃)₂(P′F₂Br)](1); this rearranges at 215 K to [RhBr₂(CO)(PEt₃)₂(P′F₂)](2). In the analogous iodide system the only product detected was of type (2). Reaction between PF₂Cl and [Rh(CO)Cl(PEt₃)₂] at 190 K gave [Rh(CO)Cl(PEt₃)₂(P′F₂Cl)]; at room temperature the main initial products were PF₃ and [Rh(CO)Cl₂(PEt₃)₂(P′FCl)](3), and on prolonged standing (3) was converted into [Rh(CO)Cl₂(PEt₃)₂(P′Cl₂)](4), also prepared from [Rh(CO)Cl(PEt₃)₂] and PCl₃. Reaction between [Ir(CO)Cl(PEt₃)₂] and an excess of PF₂Cl over a prolonged period at room temperature gave iridium analogues of first (3) and then (4). Reaction between compound (4) and [Ir(CO)Cl(PEt₃)₂] gave the iridium analogue of (4) and [Rh(CO)Cl(PEt₃)₂].