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Updated: Jun 6, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
A cationic Rh(III) complex that efficiently catalyzes hydrogen isotope exchange in hydrosilanes
Jesús Campos1, Ana C Esqueda, Joaquín López-Serrano
1Departamento de Química Inorgánica-Instituto de Investigaciones Químicas, Universidad de Sevilla-Consejo Superior de Investigaciones Científicas, Avda. Américo Vespucio 49, Isla de la Cartuja, 41092 Sevilla, Spain.
Abstract:
The synthesis and structural characterization of a mixed-sandwich (η(5)-C(5)Me(5))Rh(III) complex of the cyclometalated phosphine PMeXyl(2) (Xyl = 2,6-C(6)H(3)Me(2)) with unusual κ(4)-P,C,C',C'' coordination (compound 1-BAr(f); BAr(f) = B(3,5-C(6)H(3)(CF(3))(2))(4)) are reported. A reversible κ(4) to κ(2) change in the binding of the chelating phosphine in cation 1(+) induced by dihydrogen and hydrosilanes triggers a highly efficient Si-H/Si-D (or Si-T) exchange applicable to a wide range of hydrosilanes. Catalysis can be carried out in an organic solvent solution or without solvent, with catalyst loadings as low as 0.001 mol %, and the catalyst may be recycled a number of times.
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