Heterobimetallic [Ru(II)/Fe(II)] complexes: On the formation of trans- and cis-[RuCl2(dppf)(diimines)]

The synthesis and characterization of trans/cis-[RuCl2(dppf)(diimines)], dppf = 1,1′-bis(diphenylphosphino)ferrocene; diimines = 2,2′-bipyridine (trans/cis-(1)), the new complexes with 4,4′-dimethyl-2,2′-bipyridine (trans/cis-(2)) and 1,10-phenanthroline (cis-(3)) are presented. The complexes were synthesized using two routes and the trans/cis-isomer formation is dependent upon conditions and the precursor applied. The trans-isomer (kinetic) readily isomerizes to the cis-isomer (thermodynamic) when exposed to light (fluorescent) and this process was followed by cyclic voltammetry and UV–vis. The electrochemical studies on these complexes reveal that Fe(III)/Fe(II) couples are insensitive to the isomer (trans/cis) formed, but the Ru(III)/Ru(II) couples are dependent on the isomer. Transfer-hydrogenation reactions for reduction of acetophenone were conducted using complexes cis-(1) and cis-(2) and the results are compared with that obtained for similar complexes. X-ray structure for cis-(3) are presented and discussed.

Graphical abstractThe synthesis and characterization of trans/cis-[RuCl2(dppf)(diimines)], dppf = 1,1′-bis(diphenylphosphino)ferrocene; diimines = 2,2′-bipyridine (trans/cis-(1)), 4,4′-dimethyl-2,2′-bipyridine (trans/cis-(2)) and 1,10-phenanthroline (cis-(3)) are presented. The trans-isomer readily isomerizes to the cis-isomer when exposed to light and this process was followed by cyclic voltammetry and UV–vis. Transfer-hydrogenation reactions for reduction of acetophenone were conducted.Figure optionsDownload full-size imageDownload as PowerPoint slide