Design and Synthesis of Chiral Heteroleptic Rhodium(II) Carboxylate Catalysts: Experimental Investigation of Halogen Bond Rigidification Effects in Asymmetric Cyclopropanation

A general method for the synthesis of chiral heteroleptic rhodium­(II) tetracarboxylate catalysts is reported. The chlorinated TCPT unit was found to be an efficient polarity-control group, allowing the isolation of each complex from a mixture of six possible products. This approach contributes to enlarging the scope of accessible chiral Rh­(II) catalysts and allowed further study of the halogen bond rigidification effect observed in chlorinated complexes