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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
Coverbild
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Jahr 2019
Sprache Englisch
Identifikator ISSN: 2041-6520, 2041-6539
KITopen-ID: 1000099016
HGF-Programm 43.21.04 (POF III, LK 01)
Erschienen in Chemical science
Band 10
Heft 34
Seiten 7937–7945
Vorab online veröffentlicht am 08.07.2019
Nachgewiesen in Scopus
Web of Science
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