Iminophosphorane-based [P₂N₂] rhodium complexes

Antoine Buchard, Elina Payet, Audrey Auffrant, Xavier Le Goff, Pascal Le Floch

OAI: oai:purehost.bath.ac.uk:publications/72a63680-7532-4d04-9367-a261cdfb7af5 • DOI: https://doi.org/10.1039/C0NJ00299B

[Rh(P2N2)X] complexes (2-X, X = Cl, BF4) featuring a tetradentate iminophosphorane phosphine ligand were synthesised and characterised. X-Ray analysis provides evidence for a square planar geometry without coordination of the chloride anion. These complexes proved to be air-sensitive, and their oxidation to Rh(iii) complexes 3-X was observed in air. The controlled reaction of 2-BF4 with one equivalent of hexachloroethane yielded [Rh(P2N2)Cl2(BF4)] (3-BF4). Direct synthesis of 3-Cl can also be achieved by coordination of the [P2N2] ligand to [RhCl(THT)3] (THT = tetrahydrothiophene). The reactivity of Rh(i) complexes 2 was further investigated, and no reaction was observed with silanes, aryl halides, or pinacolborane, although decomposition was observed under 1 atm of H2 upon prolonged heating. Interestingly, reduction of complex 3-Cl was observed by NMR upon treatment with silanes or sodium isopropoxide. Therefore, complex 3-Cl was used for catalytic transfer hydrogenation of polar bonds. The reduction of aromatic and aliphatic ketones can be carried out using 1% catalyst and 10% sodium isopropoxide, while imines are partially reduced under these conditions.