Synthesis, characterization and evaluation of heterobimetallic Fe(II)/Rh(I) and Fe(II)/Ru(II) complexes as catalyst precursors for hydroformylation of 1-octene

Two new ferrocenyl iminopyridyl ligands, L1 and L2, have been synthesized and characterized using spectroscopic and analytical techniques. Both ligands were used to prepare new Rh(I) and Ru(II) ferrocenyl complexes 1–4. The structures of the complexes were confirmed using 1H and 13C nuclear magnetic resonance spectroscopy, high resolution electrospray ionization mass spectrometry, and infrared spectroscopy. The complexes were tested as catalysts in the hydroformylation of 1-octene. Rh ferrocenyl complexes 1 and 4 produced aldehydes under mild conditions while the Ru-ferrocenyl complexes 2 and 3 required higher temperature and pressure for effective hydroformylation to occur. The catalysts display excellent aldehyde chemoselectivity with varying regeoselectivity depending on temperature and pressure conditions employed. At high temperatures, the Rh ferrocenyl precatalysts favor formation of branched aldehydes due to increased isomerization at high temperatures. The Ru ferrocenyl precatalysts displayed less hydroformylation activity; however, the complexes show good chemoselectivity for aldehydes with no hydrogenation products formed.