Rhodium(i) complexes derived from tris(isopropyl)-azaphosphatrane-controlling the metal-ligand interplay.
| Autor: | Chang WC; Max Planck Institute for Chemical Energy Conversion Stiftstr. 34-36 45470 Mülheim an der Ruhr Germany christophe.werle@cec.mpg.de.; Ruhr University Bochum Universitätsstr. 150 44801 Bochum Germany., Deufel F; Max-Planck-Institut für Kohlenforschung Kaiser-Wilhelm-Platz 1 D-45470 Mülheim an der Ruhr Germany., Weyhermüller T; Max Planck Institute for Chemical Energy Conversion Stiftstr. 34-36 45470 Mülheim an der Ruhr Germany christophe.werle@cec.mpg.de., Farès C; Max-Planck-Institut für Kohlenforschung Kaiser-Wilhelm-Platz 1 D-45470 Mülheim an der Ruhr Germany., Werlé C; Max Planck Institute for Chemical Energy Conversion Stiftstr. 34-36 45470 Mülheim an der Ruhr Germany christophe.werle@cec.mpg.de.; Ruhr University Bochum Universitätsstr. 150 44801 Bochum Germany. |
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| Jazyk: | angličtina |
| Zdroj: | RSC advances [RSC Adv] 2021 Nov 22; Vol. 11 (59), pp. 37383-37391. Date of Electronic Publication: 2021 Nov 22 (Print Publication: 2021). |
| DOI: | 10.1039/d1ra07126b |
| Abstrakt: | Proazaphosphatranes are intriguing ligand architectures comprising a bicyclic cage of flexible nature. They can undergo structural deformations due to transannulation while displaying modular electronic and steric properties. Herein, we report the synthesis and coordination chemistry of rhodium(i) complexes bearing a tris(isopropyl)-azaphosphatrane (T i PrAP) ligand. The molecular structure of the primary complex (1) revealed the insertion of the metal center into a P-N bond of the ligand. The addition of a Lewis acid, i.e. , lithium chloride, promoted the dynamic behavior of the complex in the solution, which was studied by state-of-the-art NMR spectroscopy. Substituting the cyclooctadiene ligand at the metal center with triphenylphosphine or 2-pyridyldiphenylphosphine unveiled the adaptive nature of the T i PrAP backbone capable of switching its axial nitrogen from interacting with the phosphorus atom to coordinate the rhodium center. This led the entire ligand edifice to change its binding to rhodium from a bidentate to tridentate coordination. Altogether, our study shows that introducing a T i PrAP ligand allows for unique molecular control of the immediate environment of the metal center, opening perspectives in controlled bond activation and catalysis. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.) |
| Databáze: | MEDLINE |
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