Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolution

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 30, 2025

Metal-centered chirality has been recognized for over one century, and stereogenic-at-metal complexes where is exclusively attributed to the metal center due specific coordination pattern of achiral ligands around ion, broadly utilized in diverse areas natural science. However, synthesis these molecules remains constrained. Notably, while asymmetric catalysis played a crucial role production optically active organic molecules, its application less straightforward. In this study, we introduce kinetic resolution strategy employing Pd-catalyzed Suzuki-Miyaura cross-coupling reaction that efficiently produces stereogenic-at-iridium from racemic mixtures with high selectivity (achieving an s-factor up 133). This method enables further relevant chiral metallodrugs photosensitizers, underscoring practical utility our approach. Mechanistic studies suggest reductive elimination likely turnover-limiting step cross-coupling.

Language: Английский

Influence of Iodine Substitutions on the Photophysical Properties of Rhenium(I) Tricarbonyl Complexes With Pyridine Schiff Base (PSB‐IHB)

International Journal of Quantum Chemistry, Journal Year: 2025, Volume and Issue: 125(2)

Published: Jan. 8, 2025

ABSTRACT This theoretical investigation aims to evaluate the influence of iodine substitutions on phenolic moiety pyridine Schiff bases harboring an intramolecular hydrogen bond (PSB‐IHB) ancillary ligand within monocationic. fac ‐[Re(CO) 3 (N,N)(PSB‐IHB)] + architecture photophysical properties, particularly emission range. Optimized structures two Re(I) tricarbonyl complexes (C1 and C2) were analyzed, revealing a distorted octahedral coordination geometry. Geometric parameters compared with experimental data from analogous complexes. NBO analysis confirmed presence bonds (IHBs) in both singlet triplet states, providing significant stabilization. Theoretical calculations predicted three distinct absorption bands for all dichloromethane, indicating substantial electronic delocalization between pyridinic rings via azomethine group. These findings underscore crucial role donor–acceptor interactions stabilizing their impact properties. Emissions calculated C1 C2 observed range 632–643 nm. The IHBs was found be essential modulating emissions attributed ligand‐to‐ligand charge transfer transitions.

Language: Английский