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Reactions of the ruthenium(II) precursors [RuCl2(C6H6)]2 and [RuI2(p-cymene)]2 with the aminophosphine phosphinite ligands (AMPP) (S)-Cy,Cy-ProNOP and (S)-Ph,Ph-ProNOP gave the cationic complexes [RuCl(C6H6){(S)-Cy,Cy-ProNOP}]Cl 1, [RuCl(C6H6){(S)-Ph,Ph-ProNOP}]Cl 2, and [RuI(p-cymene){(S)-Ph,Ph-ProNOP}]l 3 in good to high yields. The reactions proceed in two steps via a monodentate intermediate in which the PO moiety of the AMPP diphosphine coordinates to the ruthenium prior to the chelation through PN coordination, giving the expected bidentate complexes. Neutral complexes have been synthesized starting from the Ru(COD)(2-methylallyl)2 precursor. Accordingly, complexes Ru{(S)-Ph,Ph-ProNOP}(2-methylallyl)2 4 and Ru{(S)-Ph,Ph-oxoProNOP}(2-methylallyl)2 5 are obtained through reaction with (S)-Ph,Ph-ProNOP and (S)-Ph,Ph-oxoProNOP, respectively, by progressive precipitation in the reaction mixtures. X-ray data are given for the neutral methylallyl complex Ru{(S)-Ph,Ph-ProNOP}(2-methylallyl)2 4. Complexes Ru{(S)-Cy,Cy-ProNOP}(OCOCH3)2 6 and Ru{(S)-Cy,Cy-ProNOP}(OCOCF3)2 7 were obtained through substitution of the COD ligand in Ru(COD)(OCOCH3)2 and Ru2(COD)2(OCOCF3)4, respectively. Neutral acetato and trifluoroacetato complexes Ru{(S)-Ph,Ph-ProNOP}(OCOCH3)2 8, Ru{(S)-Ph,Ph-oxoProNOP}(OCOCH3)2 9, Ru{(S)-Ph,Ph-ProNOP}(OCOCF3)2 10, and Ru{(S)-Ph,Ph-oxoProNOP}(OCOCF3)2 11 were synthesized through protonation of the corresponding methylallyl ruthenium complexes with the appropriate hydracid. All the catalyst precursors synthesized are mixtures of diastereoisomers and have been applied in asymmetric hydrogenation of three alpha-functionalized ketones, i.e., dihydro-2,4-dimethyl-2,3-furandione 12, ethylpyruvate 13, and methylbenzoylformate 14. Enantiomeric excesses (ee) up to 79.5, 63, and 48% were obtained, respectively, for the three substrates. CNRS-Gauthier-Villars.
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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI