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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[triple bond, length as m-dash]C bonds of the trop ligand. This reaction is chemoselective and converts C[triple bond, length as m-dash]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 H2 activation by interfacial sites of heterogeneous Rh/C catalysts.

SUBMITTER: Jurt P 

PROVIDER: S-EPMC6788510 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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Supporting two metal binding sites by a tailored polydentate trop-based (trop = 5<i>H</i>-dibenzo[<i>a</i>,<i>d</i>]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[triple bond, length as m-dash]C bonds of the trop ligand. This reaction is chemoselective and converts C[triple bond, length as m-dash]C bonds to a bridging carbene and an olefinic li  ...[more]

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