We describe the synthesis and X-ray crystal structure of µ-oxo-bis[(octacosafluoro-meso-tetraphenylporphyrinato)iron(III)] [(FeTPPF28)2O]. This novel iron complex is an efficient catalyst for oxidative biaryl coupling reactions of diarylamines and carbazoles. The asymmetric...

We describe an iron‐catalyzed asymmetric oxidative C−C coupling of diarylamines which proceeds at room temperature with air as final oxidant. Using hexadecafluorophthalocyanine‐iron(II) as catalyst in the presence of catalytic amounts of an axially chiral biaryl phosphoric acid, the resulting chiral 2,2′‐diamino‐1,1′‐biaryls are obtained in up to 90 % ee as confirmed by chiral HPLC. A detailed mechanism has been proposed with a radical cation‐chiral phosphate ion pair as key intermediate leading to the observed asymmetric induction.