Universität zu Köln

Liebing, Phil ORCID: 0000-0002-4660-1691, Kalim, Jorna ORCID: 0000-0003-4207-0085, Arefyeva, Natalia, Oehler, Florian, Wickleder, Mathias ORCID: 0000-0002-8864-4227 and Togni, Antonio ORCID: 0000-0003-3868-1799 (2019). A Tunable Trifluoromethyliodonium Reagent. Angew. Chem.-Int. Edit., 58 (25). S. 8585 - 8589. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3773

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Abstract

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 [Ti2Cl6(L)(4)]Cl-2 (2a) and Ti2Cl8(L) (2b). 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<2TiCl(4). Complexes 2a, 3, and 4 are remarkably bench-stable forms of activated reagent 1, while 2b is readily accessible in situ. 2a and 2b 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.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Liebing, Phil UNSPECIFIED orcid.org/0000-0002-4660-1691 UNSPECIFIED Kalim, Jorna UNSPECIFIED orcid.org/0000-0003-4207-0085 UNSPECIFIED Arefyeva, Natalia UNSPECIFIED UNSPECIFIED UNSPECIFIED Oehler, Florian UNSPECIFIED UNSPECIFIED UNSPECIFIED Wickleder, Mathias UNSPECIFIED orcid.org/0000-0002-8864-4227 UNSPECIFIED Togni, Antonio UNSPECIFIED orcid.org/0000-0003-3868-1799 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-137682
DOI:	10.1002/anie.201903623
Journal or Publication Title:	Angew. Chem.-Int. Edit.
Volume:	58
Number:	25
Page Range:	S. 8585 - 8589
Date:	2019
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1521-3773
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language COMPLEXES Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/13768