Aryl-based ferrocenyl phosphine ligands in the rhodium(I)-catalyzed hydroformylation of olefins

• Aryl-based ferrocenyl phosphine [Fe{1-PPh2(spacer)-2-NMe2CH2C5H3}(C5H5)] ligands.
• Rhodium(I)-catalyzed hydroformylation of styrene, allylbenzene and 1-hexene.
• Higher chemo- and regioselectivity than with rhodium(I) catalyst precursors alone.
• 31P{1H} NMR of phosphine selenides for elucidating the σ-donor properties.

Ferrocenyl-based phosphine ligands [Fe{1-PPh2(spacer)-2-NMe2CH2C5H3}(C5H5)] (spacer = 1,4-phenylene (rac-1), 1,3-phenylene (rac-2), 4,4′-biphenylene (rac-3), 2,5-thienylene (rac-4)) were applied in the rhodium(I)-catalyzed hydroformylation of various olefins (styrene, allylbenzene and 1-hexene) with higher chemo- and regioselectivity than a rhodium(I) catalyst precursor alone. The different σ-donor properties of rac-1–4 were elucidated by 31P{1H} NMR spectroscopy of the corresponding selenides.

Catalytic properties of new ferrocenyl-based phosphine ligands rac-[Fe{1-PPh2(spacer)-2-NMe2CH2C5H3}(C5H5)] (spacer = 1,4-or 1,3-phenylene, 4,4′-biphenylene, 2,5-thienylene) were studied in the rhodium(I)-catalyzed hydroformylation of styrene, allylbenzene and 1-hexene. The studies presented here illustrate the influence of the substituents on the phosphorus atom on the activity and the selectivity.Figure optionsDownload high-quality image (114 K)Download as PowerPoint slide