A Tunable Trifluoromethyliodonium Reagent

Four complexes of MCl₄ (M=Ti, Zr, Hf) with the hypervalent trifluoromethyl iodine reagent trifluoromethyl-1,3-dihydro-3,3-dimethyl-1,2-benziodoxole (1,=L) are described. With TiCl₄ , an I-O bond cleavage occurs, leading to the formation of the trifluoromethyliodonium alcoholate complexes [Ti₂ Cl₆ (L)₄ ]Cl₂ (2 a) and Ti₂ Cl₈ (L) (2 b). Reactions with ZrCl₄ and HfCl₄ form the complexes ZrCl₄ (L)₂ (3) and HfCl₄ (L)₂ (4), respectively, wherein the original I-O bond is retained and elongated compared to that in free 1. Therefore, the reactivity of 1 can be easily and practically fine-tuned by addition of different metal chlorides, following the order ZrCl₄ /HfCl₄ <TiCl₄ <2 TiCl₄ . Complexes 2 a, 3, and 4 are remarkably bench-stable forms of activated reagent 1, while 2 b is readily accessible in situ. 2 a and 2 b represent the first "real" trifluoromethyliodonium reagents derived from iodanes, that is, with the I-O bond being completely cleaved. The new complexes were shown to be useful for the trifluoromethylation of para-toluenesulfonate under aprotic conditions.