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Issue 34, 2019
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Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh–H intermediates

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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.

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

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Supplementary files

Article information


Submitted
02 Jun 2019
Accepted
05 Jul 2019
First published
08 Jul 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 7937-7945
Article type
Edge Article

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

P. Jurt, O. G. Salnikov, T. L. Gianetti, N. V. Chukanov, M. G. Baker, G. Le Corre, J. E. Borger, R. Verel, S. Gauthier, O. Fuhr, K. V. Kovtunov, A. Fedorov, D. Fenske, I. V. Koptyug and H. Grützmacher, Chem. Sci., 2019, 10, 7937
DOI: 10.1039/C9SC02683E

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