Abstract

Four new chiral PNP′ pincer ligands with a scaffold consisting of a planar chiral ferrocene and a centro chiral aliphatic unit were synthesized and characterized. Treatment of anhydrous FeBr2(THF)2 with 1 equiv of the unsymmetrical chiral PNP′ pincer ligands afforded complexes of the general formula [Fe(PNP′)Br2]. In the solid state these complexes adopt a tetrahedral geometry with the PNP′ ligands coordinated in a κ2P,N-fashion, as shown by X-ray crystallography. These complexes react with CO in the presence of NaBH4 to yield hydride complexes of the type [Fe(PNP′)(H)(Br)(CO)], which were isolated and tested as catalysts in the asymmetric hydrogenation of ketones. Enantioselectivities of up to 81% ee were obtained.

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