Dirhodium (II) paddlewheel complexes are renowned for their ability to catalyze a variety of insertion-based reactions. Commonly, most modification of the catalysts involve the exchanging of the bridging ligands resulting in vast changes in reactivity and enantioselectivity. More recently, coordination of molecules to one of the open axial sites have also been shown to be beneficial to chemo/enantioselectivity. Our research aims to probe the benefits of axial coordination using a thioether-functionalized tether present on a bridging ligand. We have synthesized ligands derived from amino acids that contain a thioether and have incorporated those ligands onto chiral dirhodium (II) catalysts. The sulfur present on the tether allows for controlled coordination to the axial site which in turn can donate electron density into the rhodium complex. This allows the complex to “tame”, or stabilize, more reactive carbenoid intermediates, resulting in more selective reactions. This poster outlines the synthesis and characterization of new chiral rhodium paddlewheel complexes containing axially coordinated thioethers and their catalytic activity in Si-H insertion reactions.

Exploring axial coordination of ligands in dirhodium (II) paddlewheel complexes in Si-H insertion reactions

255th National Meeting (2018)

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