Monofluorophos-Metal Complexes: Ripe for Future Discoveries in Homogeneous Catalysis

• Published in: Molecules (Basel, Switzerland) Vol. 29; no. 10; p. 2368
• Main Authors: Miles-Hobbs, Alexandra M, Pringle, Paul G, Woollins, J Derek, Good, Daniel
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 17.05.2024
• Subjects: Catalysis; Chemistry; coordination chemistry; fluorophosphines; fluorophosphites; homogeneous catalysis; Hydrolysis; Ligands; fluorophosphites; homogeneous catalysis; fluorophosphines; coordination chemistry
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules29102368

The discovery that cyclic (ArO) PF can support Rh-catalysts for hydroformylation with significant advantages in tuning regioselectivity transformed the study of metal complexes of monofluorophos ligands from one of primarily academic interest to one with potentially important applications in catalysis. In this review, the syntheses of monofluorophosphites, (RO) PF, and monofluorophosphines, R PF, are discussed and the factors that control the kinetic stability of these ligands to hydrolysis and disproportionation are set out. A survey of the coordination chemistry of these two classes of monofluorophos ligands with d-block metals is presented, emphasising the bonding of the fluorophos to d-block metals, predominantly in low oxidation states. The application of monofluorophos ligands in homogeneous catalysis (especially hydroformylation and hydrocyanation) is discussed, and it is argued that there is great potential for monofluorophos complexes in future catalytic applications.