Ambidentate sulfoxide ligands may undergo redox-induced linkage isomerism (RILI) or photoisomerism when bound to Ru(II) centers:  Such complexes have potential applications as molecular switches.  To target chiroptical molecular switches, chiral tetradentate N,N'-(�-ethylsulfinyl)diamine ligands have been synthesized by the reaction of (R)-p-tolyl vinyl sulfoxide with secondary diamines derived from ethylene diamine or 1,2-cyclohexanediamine.  Octahedral Ru(II) dichloride complexes of some of these ligands have been prepared by their reaction with RuCl2(PPh3)3, and at least one example of each possible metal complex geometric isomer isolated.  All structures were confirmed by a combination of single crystal X-ray structures, and NMR, UV-vis and CD spectroscopic studies.  Cyclic voltammetry reveals that only the cis-� isomers show the scan-rate dependent behavior consistent with RILI upon oxidation to Ru(III).  The kinetic and thermodynamic parameters associated with these processes have been analyzed and will be discussed along with the electronic requirements for RILI in this type of complex.

Redox-induced linkage isomerism and geometric isomerism in Ru(II) dichloride complexes of chiral tetradentate aminosulfoxide ligands

243rd National Meeting (2012)

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