α-Fluorinated cyclic amidophosphite ligands. Their synthesis, Rh complexes and catalytic activity in the hydroformylation of styrene

The synthetic approaches to cyclic phosphite and amido(diamido)phosphite ligands bearing the residues of electron withdrawing perfluorinated tails at the β-position to the phosphorus atom have been elaborated. Catalytic systems based on rhodium complexes of these ligands formed in situ using Rh(CO)2(acac) as a catalytic precursor demonstrate high activity in the hydroformylation of styrene along with good selectivity in respect to branched aldehyde. Quantum-chemical calculations proved that both the rate of the formation of branched alkyl complex, as well as its reactivity are influenced by the steric and electronic parameters in the same manner.

The synthetic routes to both benzoanellated (3a,b, 5a–e) and monocyclic (8a–c, 9a–c, 14a–g) (amido)phosphate ligands with fluorine containing substituents were elaborated. Their Rh(I) complexes formed in situ demonstrate high activity in the hydroformylation of styrene along with selectivity in respect to branched aldehyde. The “structure–activity” relationship was estimated using quantum-chemical calculations.Figure optionsDownload as PowerPoint slide