NNN pincer and NN bidentate(pyrazolylpyridyl) Rh(I) complexes as catalyst precursors for hydroformylation of olefins

Abstract

The industrial process of hydroformylation or the oxo process has been used for many years in the production of aldehydes from alkenes. Different metals have been used as efficient catalysts for hydroformylation, in which linear and branched aldehydes are the products obtained; therefore, the development of new catalysts for hydroformylation with high selectivity to aldehydes is important. Rhodium complexes 69 were synthesized using [RhCl(CO)2]2, or [RhCl(COD)]2, with either pyrazolylpyridyl NNN pincer ligands or a pyrazolylpyridyl NN ligand. These complexes were then evaluated as catalyst precursors in the hydroformylation reaction using a variety of alkenes. The catalysts all showed activity in hydroformylation but the most active catalyst was methyl-substituted pyrazolyl–rhodium complex 7 following optimization of temperature, syngas pressure and amount of catalyst. Other olefinic substrates were used for hydroformylation in the presence of 7 under the optimum hydroformylation conditions. Undecene and dodecene as substrates only showed minimal formation of aldehydes with predominantly isomerization of the alkene being observed.

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Acknowledgements

We acknowledge the National Research Foundation of South Africa (NRF) (Grant Nos. 105557, 117989), The Technology and Human Resource for Industry Programme (THRIP), (Grant No. THRIP/58/30/11/2017), Sasol SA Ltd (University Collaboration Programme) and the University of Johannesburg’s Centre for Synthesis and Catalysis for financial support.

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Correspondence to Banothile C. E. Makhubela.

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Gamede, N.V., Kapfunde, T.A., Ocansey, E. et al. NNN pincer and NN bidentate(pyrazolylpyridyl) Rh(I) complexes as catalyst precursors for hydroformylation of olefins. Transit Met Chem 45, 1–8 (2020). https://doi.org/10.1007/s11243-019-00350-2

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