Universität zu Köln

Shreiber, Scott T., Amin, Fatema ORCID: 0000-0002-8420-1912, Schafer, Sascha A., Cramer, Roger E., Klein, Axel ORCID: 0000-0003-0093-9619 and Vicic, David A. (2022). Synthesis, structure, and electrochemical properties of [LNi(R-f)(C4F8)](-) and [LNi(R-f)(3)](-) complexes. Dalton Trans., 51 (14). S. 5515 - 5524. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1477-9234

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Abstract

The new anionic nickelate complexes [(MeCN)Ni(C4F8)(CF3)](-), [(MeCN)Ni(C4F8)(C2F5)](-), [(IMes)Ni(C4F8)(CF3)](-), [(IMes)Ni(CF3)(3)](-) (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), and [(F-NHC)Ni(R-f)(3)](-) (F-NHC = 1,3-bis(2,4-F2Ph), 2,4,6-F3Ph- or 3,4,5-F3Ph)imidazol-2-ylidene; (R-f = CF3 or C2F5) were synthesized and structurally characterized. The electrochemical properties of all new compounds were revealed by cyclic voltammetry studies and compared to the known CF3 analogue [(MeCN)Ni(CF3)(3)](-). The IMes-coordinated complexes exhibited initial oxidation events that were well-separated from a second oxidation process in the cyclic voltammograms. The complexes containing F-substituted NHC ligands [(F-NHC)Ni(CF3)(3)](-) are structurally quite similar to the IMes derivative and reveal also two separated oxidation waves in their cyclic voltammograms. The absolute potentials as well as the separation between the two waves vary with the substitution pattern, suggesting that the NHC ligand environment (NHC = N-heterocyclic carbene) is an interesting platform for the development of new redox-triggered reactions that release trifluoromethyl and perfluoroalkyl radicals upon oxidation.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Shreiber, Scott T. UNSPECIFIED UNSPECIFIED UNSPECIFIED Amin, Fatema UNSPECIFIED orcid.org/0000-0002-8420-1912 UNSPECIFIED Schafer, Sascha A. UNSPECIFIED UNSPECIFIED UNSPECIFIED Cramer, Roger E. UNSPECIFIED UNSPECIFIED UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED Vicic, David A. UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-674620
DOI:	10.1039/d2dt00511e
Journal or Publication Title:	Dalton Trans.
Volume:	51
Number:	14
Page Range:	S. 5515 - 5524
Date:	2022
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1477-9234
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language NICKEL-CATALYZED DIFLUOROMETHYLATION; (HETERO)ARYL BROMIDES; TRIFLUOROMETHYLATION; DIFLUOROALKYLATION; ACIDS Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/67462