| Title: |
Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates |
| Authors: |
Jurt, Pascal; Salnikov, Oleg G.; Gianetti, Thomas L.; Chukanov, Nikita V.; Baker, Matthew G.; Le Corre, Gregoire; Borger, Jaap E.; Verel, Rene; Gauthier, Sebastien; Fuhr, Olaf; Kovtunov, Kirill V.; Fedorov, Alexey; Fenske, Dieter; Koptyug, Igor V.; Grutzmacher, Hansjorg |
| Contributors: |
Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology Zürich (ETH Zürich); Russian Academy of Sciences Moscow (RAS); Novosibirsk State University (NSU); University of Arizona; Institut des Sciences Chimiques de Rennes (ISCR); Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes); Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS); Karlsruhe Institute of Technology = Karlsruher Institut für Technologie (KIT); Swiss National Science FoundationSwiss National Science Foundation (SNSF); Russian Science FoundationRussian Science Foundation (RSF) 19-13-00172; SB RAS integrated research program 0333-2018-0006/II.1.13; Holcim Stiftung |
| Source: |
ISSN: 2041-6520. |
| Publisher Information: |
HAL CCSD; The Royal Society of Chemistry |
| Publication Year: |
2019 |
| Collection: |
Université de Rennes 1: Publications scientifiques (HAL) |
| Subject Terms: |
[CHIM.COOR]Chemical Sciences/Coordination chemistry |
| Description: |
International audience ; 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 and xe002;C bonds of the trop ligand. This reaction is chemoselective and converts C and 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. |
| Document Type: |
article in journal/newspaper |
| Language: |
English |
| Relation: |
info:eu-repo/semantics/altIdentifier/pmid/31673319; PUBMED: 31673319 |
| DOI: |
10.1039/c9sc02683e |
| Availability: |
https://univ-rennes.hal.science/hal-02303398; https://univ-rennes.hal.science/hal-02303398v1/document; https://univ-rennes.hal.science/hal-02303398v1/file/c9sc02683e.pdf%3B; https://doi.org/10.1039/c9sc02683e |
| Rights: |
info:eu-repo/semantics/OpenAccess |
| Accession Number: |
edsbas.55FE8E3A |
| Database: |
BASE |