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Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates

Abstract : Supporting two metal binding sites by a tailored polydentate trop-based (trop = 5H-dibenzo[a,d]cyclohepten-5-yl) ligand yields highly unsymmetric homobimetallic rhodium(i) complexes. Their reaction with hydrogen rapidly forms Rh hydrides that undergo an intramolecular semihydrogenation of two C and xe002;C bonds of the trop ligand. This reaction is chemoselective and converts C and xe002;C bonds to a bridging carbene and an olefinic ligand in the first and the second semihydrogenation steps, respectively. Stabilization by a bridging diphosphine ligand allows characterization of a Rh hydride species by advanced NMR techniques and may provide insight into possible elementary steps of H-2 activation by interfacial sites of heterogeneous Rh/C catalysts.
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Pascal Jurt, Oleg G. Salnikov, Thomas L. Gianetti, Nikita V. Chukanov, Matthew G. Baker, et al.. Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates. Chemical Science , The Royal Society of Chemistry, 2019, 10 (34), pp.7937-7945. ⟨10.1039/c9sc02683e⟩. ⟨hal-02303398⟩

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