Comparison of the Reactivity of M(allyl)3 (M = Rh, Ir) with Donor Ligands
摘要:
Reactions of M(allyl)(3) [M = Rh, Ir] with a variety of donor ligands have been investigated. While both complexes are unreactive toward "hard" N- and O-donor ligands, "soft" ligands such as tolylisothiocyanate, tertiary phosphines, CO, and aryl isocyanides are readily added. Whereas ligand additions to Rh(allyl)(3) are often accompanied by reduction of the Rh(III) center, analogous reactions with Ir(allyl)(3) afford stable trivalent products containing sigma -allyl ligands. The molecular structures of several derivatives are presented, including Ir(sigma -allyl)(pi -allyl)(2)(PPh3), Ir(sigma -allyl)(2)(pi -allyl)(PMe3)(2), and Ir(sigma -allyl)(3)(C dropN-2,6-Me2C6H3)(3).
Ru and Rh nanoparticles (NPs) RuI, RuII, RhI and RhII, stabilised by triphenylphosphine (PPh3) and diphenylphosphinobutane (dppb) were synthesised, characterised and applied as catalysts in the hydrogenation of several aromaticketones. The effects of the nature of the metal and of the stabilising agent on the aryl versus ketonehydrogenation were studied. For Rh NPs, the coordination of arene dominates