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A novel approach to the design of dirhodium(II) tetracarboxylates derived from (S)‐amino acid ligands is reported. The approach is founded on tailoring the steric influences of the overall catalyst structure by reducing the local symmetry of the ligand's N‐heterocyclic tether. The application of the new approach has led to the uncovering of [Rh2(S‐tertPTTL)4] as a new member of the dirhodium(II) family...
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