Stereospecific control of metal-centered chirality in ruthenium complexes bearing a tetradentate N2N’P ligand

Resumen del póster presentado a la XXXVIII Reunión Bienal de la Real Sociedad Española de Química, celebrada en el Palacio de Congresos de Granada, del 27 de junio al 30 de junio de 2022.Polydentate ligands and their complexes are of high interest to organometallic and organic chemists, as they are widely and successfully applied in homogeneous catalysis. For example, metal complexes of pincer ligands are very useful in the development of clean and sustainable energy carriers. On the other hand, a new methodology based on the use of achiral bidentate ligands to design octahedral chiral-at-metal complexes has recently been developed. In both cases, to provide a rational catalyst optimization, the smart design of stable and rigid configurations is particularly important. In this work, we present several routes for the synthesis of chiral-at-ruthenium(II) complexes bearing the achiral tripodal ligand N,N-bis[(pyridin-2-yl)methyl]-[2-(diphenylphosphino) phenyl]methanamine acting as tetradentate ligand. In particular, the octahedral complexes [RuCl2(κ4-N2N’P)] (1), [RuCl(κ4-N2N’P)(NCMe)][SbF6] (2) and [Ru(κ4-N2N’P)(NCMe)2][SbF6]2 (3) are obtained in good yields with complete diastereoselectivity. Only one single isomer is detected and isolated. The new compounds have been characterized by analytical and spectroscopic methods and by the X-ray determination of the crystal structures of the complexes 1-3. In addition, we have studied the behavior of complexes 2 and 3 as pre-catalysts in Diels-Alder reactions.Peer reviewe