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Metal as Source of Chirality in Octahedral Complexes with Tripodal Tetradentate Ligands
María Carmona1, Ricardo Rodríguez1, Vincenzo Passarelli1,2
1Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC - Universidad de Zaragoza , Pedro Cerbuna 12, 50009 Zaragoza, Spain.
Abstract:
The challenging control of the absolute configuration of chiral-at-metal complexes is efficiently achieved using the tripodal tetradentate ligand L. The optical resolution of rac-[RhCl2(κ4C,N,N',P-L)] mediated by (S)-α-phenylglycine provides access to enantiopure complexes of general formula [Rh(κ4C,N,N',P-L)A(Solv)][SbF6]n that enantioselectively catalyze the Diels-Alder reaction between methacrolein and HCp with enantiomeric ratio of up to >99/1. The nature of the active species, the origin of the enantioselectivity and mechanistic details are disclosed by means of NMR spectroscopy and DFT studies.
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