Rhodium(II) paddlewheel complexes are renowned for their ability as metal carbenoids to catalyze a number of transformations.  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 and selectivity 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 complexes with modified bridging ligands that contain a functionalized tether capable of coordinating to the axial position of the complex. The complexes were evaluated with known rhodium carbene cyclopropanation and insertion reactions to provide broader insight on the potential applications of tethered axial coordination.

Taming rhodium(II) carbenes with tethered, axial coordination

2019 Spring National Meeting

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