Coordination Chemistry of New Chiral P,N Ferrocenyl Ligands with Half-Sandwich Ruthenium(II), Rhodium(III), and Iridium(III) Complexes

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• 作者：Muh-Mei Wei ; Max Garcı ; ́ ; a-Melchor ; Jean-Claude Daran ; Catherine Audin ; Agust铆 Lled贸s ; Rinaldo Poli ; Eric Deydier ; Eric Manoury
• 刊名：Organometallics
• 出版年：2012
• 出版时间：September 24, 2012
• 年：2012
• 卷：31
• 期：18
• 页码：6669-6680
• 全文大小：526K
• 年卷期：v.31,no.18(September 24, 2012)
• ISSN：1520-6041

文摘

The new half-sandwich ruthenium(II), rhodium(III), and iridium(III) complexes (p-cymene)RuCl₂L and Cp*MCl₂L (M = Rh, Ir), where L is a planar chiral ferrocenyl tosylamine-phosphine ligand {1,2-(TosNRCH₂)(PPh₂)C₅H₃}FeCp (R = H, Me) coordinated in a monodentate fashion (魏¹P), have been synthesized and fully characterized both in solution (multinuclear NMR, mass spectrometry) and in the solid state (X-ray analysis on single crystals). Intra- and intermolecular N鈥揌路路路Cl bonds were observed. Variable-temperature NMR shows an equilibrium between different structures, which have been discussed with the help of DFT calculations. Addition of triethylamine to the complexes with R = H allows removing the tosylamide acidic hydrogen, giving rise to a ferrocenyl amidophosphine ligand coordinated in a bidentate fashion (魏²P,N). All complexes have been fully characterized by multinuclear NMR and mass spectrometry. The structure of the iridium complex, determined by X-ray diffraction, shows a planar nitrogen atom and a stable metal-centered chirality. Only the most stable diastereoisomer, according to DFT calculations, has been observed. A number of these complexes were assessed in the catalytic transfer hydrogenation and asymmetric transfer hydrogenation of acetophenone.