Ru(II) dichloride complexes of two different N,N'-dimethyl-N,N'-di(p-tolylsulfinylethyl)ethanediamine  type ligands occur as three different geometric isomers, designated as trans, cis-a, and cis-�.  Only one of these types, the cis-�, exhibits redox-induced linkage isomerism behavior of one of the coordinated sulfoxide ligands.  The influence of ligand structure upon isomer ratio has been further investigated by synthesizing ligands varying in the size of the N-alkyl groups, the length of the N-N linkage, and in the relative stereochemistry of backbone and sulfoxide chirality.  Reaction of these ligands with RuCl2(PPh3)3 gave isomer mixtures that are assigned by 1H NMR and UV-vis spectroscopies.  In certain cases the structural characterizations were confirmed by single crystal X-ray structures after separation of the mixtures.  These findings allow rational design of ligands that strongly favor each particular isomer type.  The application of the chiral-at-metal cis-a complexes as catalysts in asymmetric transfer hydrogenation reactions will also be presented.

Investigation of the relationship between tetradentate aminosulfoxide ligand structure and geometric isomerism in their Ru(II) dichloride complexes

245th National Meeting (2013)

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