Heterobimetallic complexes with ferrocenyl-substituted phosphaheterocycles

• A synthetic route to ferrocenyl-substituted heterophosphorinanes was developed.
• They act as bidentate P,N ligands towards Mo0 and as monodentate ligands towards RuII and AuI.
• Preliminary studies in the RhI-catalysed hydroformylation were performed.
• Hydroformylation of ethyl methacrylate showed a preference for the branched aldehyde.

The ferrocenyl-substituted phosphaheterocycles racemic 1-(1,3,2-dithiaphosphorinan-2-yl)-2-N,N-dimethylaminomethylferrocene (rac-4) and racemic 1-(1,3,2-dioxaphosphorinan-2-yl)-2-N,N-dimethylaminomethylferrocene (rac-5) have been prepared and their coordination chemistry has been studied. Compounds rac-4 and rac-5 act as bidentate P,N ligands in rac-[Mo(CO)4(4-κP,N)] (rac-6) and rac-[Mo(CO)4(5-κP,N)] (rac-7), and as monodentate ligands in rac-[RuCl2(5-κP)(η6-cymene)] (rac-8) and rac-[AuCl(4-κP)] (rac-9). Compounds rac-4 to rac-9 were fully characterised by NMR (1H, 13C, 31P) and IR spectroscopy, mass spectrometry, single-crystal X-ray crystallography, and elemental analysis. Furthermore, preliminary studies on rac-5 in the rhodium(I)-catalysed hydroformylation of ethyl methacrylate were carried out and showed a preference for the branched aldehyde.

Substitution of N,N-dimethylaminomethylferrocene (1) with phosphorinanes 2 and 3 leads to 1-(1,3,2-dithia- (rac-4) and 1-(1,3,2-dioxaphosphorinan-2-yl)-2-N,N-dimethylaminomethylferrocene (rac-5). Transition metal complexes of molybdenum, gold and ruthenium were obtained. Additionally, preliminary catalytic studies on rac-5 in the rhodium(I)-catalysed hydroformylation of ethyl methacrylate were carried out.Figure optionsDownload as PowerPoint slide