Rhodium(i) complexes derived from tris(isopropyl)-azaphosphatrane—controlling the metal–ligand interplay. Issue 59 (22nd November 2021)

• Record Type: Journal Article
• Authors: Chang, Wei-Chieh; Deufel, Fritz; Weyhermüller, Thomas; Farès, Christophe; Werlé, Christophe
• Is Part Of: RSC advances. Volume 11:Issue 59(2021)
• Page Start: 37383
• Page End: 37391
• Publication Date: 2021-11-22
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d1ra07126b
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : The synthesis and coordination chemistry of Rh(i ) complexes bearing a tris(isopropyl)-azaphosphatrane (T i PrAP) ligand are reported. The adaptive nature of T i PrAP ligands allows for molecular control of the immediate environment of the metal center. 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 (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.