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Microemulsions provide a unique opportunity to tailor the polarity and liquid confinement in asymmetric catalysis via nanoscale polar and nonpolar domains separated by a surfactant film. For chiral diene Rh complexes, the influence of counterion and surfactant film on the catalytic activity and enantioselectivity remained elusive. To explore this issue chiral norbornadiene Rh(X) complexes (X = OTf, OTs, OAc, PO 2 F 2 ) were synthesized and characterized by X-ray crystallography and theoretical calculations. These complexes were used in Rh-