A Tunable Trifluoromethyliodonium Reagent.

Liebing P; Kalim J; Arefyeva N; Oehler F; Wickleder M; Togni A

doi:10.1002/anie.201903623

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Journal article

A Tunable Trifluoromethyliodonium Reagent.

Liebing P Swiss Federal Institute of Technology, ETH Zurich, Department of Chemistry and Applied Biosciences, Vladimir-Prelog-Weg 2, 8093, Zurich, Switzerland.
Kalim J Swiss Federal Institute of Technology, ETH Zurich, Department of Chemistry and Applied Biosciences, Vladimir-Prelog-Weg 2, 8093, Zurich, Switzerland.
Arefyeva N University of Cologne, Department of Chemistry, Institute of Inorganic Chemistry, Greinstrasse 6, 50939, Cologne, Germany.
Oehler F Martin-Luther-Universität Halle-Wittenberg, Institut für Chemie, Kurt-Mothes-Strasse 2, 06120, Halle (Saale), Germany.
Wickleder M University of Cologne, Department of Chemistry, Institute of Inorganic Chemistry, Greinstrasse 6, 50939, Cologne, Germany.
Togni A Swiss Federal Institute of Technology, ETH Zurich, Department of Chemistry and Applied Biosciences, Vladimir-Prelog-Weg 2, 8093, Zurich, Switzerland.

2019-04-25

Published in:

Angewandte Chemie (International ed. in English). - 2019

English 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

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