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  Rhodium(I) complexes derived from tris(isopropyl)-azaphosphatrane—controlling the metal–ligand interplay

Chang, W.-C., Deufel, F., Weyhermüller, T., Farès, C., & Werlé, C. (2021). Rhodium(I) complexes derived from tris(isopropyl)-azaphosphatrane—controlling the metal–ligand interplay. RSC Advances, 11(59), 37383-38391. doi:10.1039/D1RA07126B.

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 Creators:
Chang, Wei-Chieh1, 2, Author
Deufel, Fritz3, Author
Weyhermüller, Thomas1, Author
Farès, Christophe3, Author              
Werlé, Christophe1, 2, Author
Affiliations:
1Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34–36, 45470 Mülheim an der Ruhr, Germany, ou_persistent22              
2Ruhr University Bochum, Universitätsstr. 150, 44801 Bochum, Germany, ou_persistent22              
3Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445623              

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 Abstract: 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 (TiPrAP) 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 TiPrAP 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 TiPrAP ligand allows for unique molecular control of the immediate environment of the metal center, opening perspectives in controlled bond activation and catalysis.

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Language(s): eng - English
 Dates: 2021-09-232021-11-062021-11-22
 Publication Status: Published online
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/D1RA07126B
 Degree: -

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Title: RSC Advances
  Abbreviation : RSC Adv.
Source Genre: Journal
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Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: - Volume / Issue: 11 (59) Sequence Number: - Start / End Page: 37383 - 38391 Identifier: ISSN: 2046-2069
CoNE: https://pure.mpg.de/cone/journals/resource/2046-2069