Chiral single-atom-bridged diphosphorus ligands: synthesis, complexation and catalysis.

Area of Science:

• Organometallic Chemistry
• Catalysis
• Asymmetric Synthesis

Background:

• Single-atom-bridged diphosphorus ligands are crucial in homogeneous catalysis.
• Enantiopure ligands are essential for stereoselective synthesis.
• Understanding ligand structure-activity relationships is key to catalyst design.

Purpose of the Study:

• To review the synthesis, complexation, and catalytic applications of enantiopure single-atom-bridged diphosphorus ligands.
• To organize information by ligand type, highlighting common structures.
• To analyze crystal structures and geometric parameters of metal complexes.

Main Methods:

• Literature review up to early 2025.
• Categorization of ligands based on bridging unit (CR2, NR, O).
• Analysis of crystallographic data for bidentate monometallic complexes.

Main Results:

• Methylene-bridged and amino-bridged diphosphorus ligands are the most prevalent.
• Detailed information on synthesis, complexation, and catalytic performance is presented.
• Crystal structure analysis provides insights into bite angles, metal-phosphorus distances, and buried volumes.

Conclusions:

• Enantiopure single-atom-bridged diphosphorus ligands are versatile tools in enantioselective catalysis.
• The review consolidates knowledge on these ligands, aiding future catalyst development.
• Structural insights from crystal data are valuable for rational catalyst design.