A Very Readily Prepared Ligand for Rhodium Catalysed Propene Hydroformylation (dataset)

The dataset contains the NMR data for the characterisation of EasyDiPhos and other related bidentate ligands. A bis-phosphoramidate ligand that can be made in just one synthetic step has been discovered that enables Rh catalysed hydroformylations to proceed with unusually low n:iso ratios. An initial ligand-design identified bis-phosphonites with some structural aspects broadly in common with class-leading phospholane-phosphite ligands. These were made in one step, did give unusually low n:iso ratios for propene hydroformylation, but were prone to hydrolysis. Bis-phosphoramidates with a dimethylhydrazine backbone were readily made, leading to the informal family name, EasyDiPhos. They were also found to have significant stability to moisture, air, and to relatively high temperatures during hydroformylation conditions. The latter was studied using a combination of High-Pressure-Infra-Red spectroscopy and NMR analysis of the catalyst resting state after one week under typical reaction conditions. Propene hydroformylation with n:iso ratios well below 1 was carried out and with turnover numbers around 1000 mol/mol/h. One of the ligands, whilst not being the most iso-selective example, had a partially flexible n:iso ratio depending on temperature and pressure. Two Pt(II) complexes were prepared and their X-ray crystal structures determined. Finally, the most iso-selective catalyst was examined using conditions more suited to laboratory-scale organic synthesis (prioritising iso-selectivity over rates). This reveals that the unusual n:iso selectivity partly transfers to other substrates, with notable selectivity in the hydroformylation of allyl benzene being an example.