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

Jurt, Pascal; Salnikov, 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

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≡C bonds of the trop ligand. This reaction is chemoselective and converts C≡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.

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Verlagsausgabe §
DOI: 10.5445/IR/1000099016
Veröffentlicht am 16.10.2019
Originalveröffentlichung
DOI: 10.1039/c9sc02683e
Scopus
Zitationen: 5
Dimensions
Zitationen: 5
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2019
Sprache Englisch
Identifikator ISSN: 2041-6520, 2041-6539
KITopen-ID: 1000099016
HGF-Programm 43.21.04 (POF III, LK 01) Molecular Engineering
Erschienen in Chemical science
Verlag Royal Society of Chemistry (RSC)
Band 10
Heft 34
Seiten 7937–7945
Vorab online veröffentlicht am 08.07.2019
Nachgewiesen in Scopus
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Web of Science
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