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].