Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh–H intermediates
Author
Jurt, PascalSalnikov, Oleg G.
Gianetti, Thomas L.
Chukanov, Nikita V.
Baker, Matthew G.
Le Corre, Grégoire
Borger, Jaap E.
Verel, Rene
Gauthier, Sébastien
Fuhr, Olaf
Kovtunov, Kirill V.
Fedorov, Alexey
Fenske, Dieter
Koptyug, Igor V.
Grützmacher, Hansjörg
Affiliation
Univ Arizona, Dept Chem & BiochemIssue Date
2019-09-14
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ROYAL SOC CHEMISTRYCitation
Chem. Sci., 2019,10, 7937-7945Journal
CHEMICAL SCIENCERights
This journal is © The Royal Society of Chemistry 2019. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.Collection Information
This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at repository@u.library.arizona.edu.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 & xe002;C bonds of the trop ligand. This reaction is chemoselective and converts C & 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.Note
Open access articleISSN
2041-6520Version
Final published versionSponsors
Swiss National Science Foundation; Russian Science Foundation [19-13-00172]; SB RAS integrated research program [0333-2018-0006/II.1.13]; Holcim Stiftungae974a485f413a2113503eed53cd6c53
10.1039/c9sc02683e
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Except where otherwise noted, this item's license is described as This journal is © The Royal Society of Chemistry 2019. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.