Oxidative additions on indenyl rhodium complexes bearing the hemilabile homoallyldiphenylphosphane (HADPP) ligand

• New indenyl rhodium(III) complexes have been synthesized.
• Oxidative addition of bromine is competitive with the bromination of the olefin.
• The pathway for the oxidative addition of MeI have been studied.

Oxidative additions of halogens and methyl iodide on complex [Rh(η5-C9H7){κ3(P,C,C′)-Ph2PCH2CH2CHCH2}] (1) have been carried out. The addition of bromine leads to the complexes [Rh(η5-C9H7)Br2{κ1(P)-Ph2PCH2CH2CHCH2}] (4) or [Rh(η5-C9H7)Br2{κ1(P)-Ph2PCH2CH2CHBrCH2Br}] (5) depending on the reaction conditions.Studies on the oxidative addition of methyl iodide show up the influence of the ring slippage of the five member ring of the indenyl ligand in these reactions.

Oxidative additions on [Rh(η5-C9H7){κ3(P,C,C′)-Ph2PCH2CH2CHCH2}] have been performed. When bromine is used as reagent, oxidative addition to the metal centre and bromination of the olefin are observed. Studies on the reaction with methyl iodide indicate that the ring slippage of the five member ring of the indenyl ligand cannot be discarded.Figure optionsDownload as PowerPoint slide