Dirhodium(II) paddlewheel complexes are renowned for their ability as metal carbenoids to catalyze insertion-based reactions. One can control the degree of reactivity and selectivity of the transformation by judicious choice of ligand. General strategies for ligand design involve modification of bridging ligands, however, additives in these reactions have been observed to coordinate to the axial sites of the catalyst and, to an extent, affect the reactivity of the catalyst. While there are current research efforts to probe the benefits of axial coordination, there is still need for robust methods to clarify their structural and electronic influence on catalyst reactivity and selectivity. We are investigating this through the synthesis of novel dirhodium(II) complexes with modified oxazolidinate bridging ligands that contain a functionalized tether capable of coordinating to the axial position of the complex. The complexes were evaluated with known dirhodium(II) carbenoid reactions to provide broader insight on the potential effects of tethered axial coordination.

Synthesis and reactivity of mixed-ligand dirhodium(II) complexes with pendant axial ligands

253rd National Meeting (2017)

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