Synthesis and Reactivity of Ruthenium(0) Complexes of MOP and Other Biaryl Monophosphine Ligands
Year: 2025
Type: article
Abstract: A one-pot synthesis of P,arene-chelated ruthenium(0) complexes from readily available [Ru( p -cymene)Cl 2 ] 2 is described. The [Ru( p -cymene)Cl 2 ] 2 precursor reacts with monophosphine ligand ( R )-2-diphenylphosphino-2′-methoxy-1,1′-binaphthyl (MOP) to form Ru( p -cymene)(MOP)Cl 2 intermediate ( 1 ), which then can be reduced under mild conditions by Zn/LiCl in the presence of stabilizing ligands PPh 3 or styrene to give zerovalent ruthenium complexes, Ru(MOP)(PPh 3 ) ( 3 ) and Ru(MOP)(styrene) ( 4 ), respectively. NMR and single-crystal X-ray diffraction studies have confirmed a σ-P/η 6 -arene coordination mode of the MOP ligand. Being Ru(0) species, complexes 3 and 4 are exceptionally thermally stable, undergoing virtually no decomposition at 100 °C over 48 h. Unlike previously reported Ru(BINAP)(PPh 3 ), the new Ru-MOP complexes are reluctant to activate C−H and N−H bonds, yet they oxidatively add aryl halides, poorly reactive PhCl included, to give Ru(MOP)(Ph)X ( 5, X = I, Br, Cl). The synthetic methodology has been extended to other biaryl phosphines P (CyJohnPhos, MePhos, DavePhos, Cy-vBRIDP) and various stabilizing ligands L (styrene, norbornene, and cyclooctadiene), providing a family of analogous σ-P/η 6 -arene Ru(0) complexes Ru( P )( L ) in moderate to good yield.
Source: Inorganic Chemistry
Institution: Wageningen University & Research
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Award: G4706878822
OpenAlex ID: W4417423113