Synthesis of Gold(I)-Trifluoromethyl Complexes and their Role in Generating Spectroscopic Evidence for a Gold(I)-Difluorocarbene Species

Sofie M P Vanden Broeck; David J Nelson; Alba Collado; Laura Falivene; Luigi Cavallo; David B Cordes; Alexandra M Z Slawin; Kristof Van Hecke; Fady Nahra; Catherine S J Cazin; Steven P Nolan

doi:10.1002/chem.202100195

Synthesis of Gold(I)-Trifluoromethyl Complexes and their Role in Generating Spectroscopic Evidence for a Gold(I)-Difluorocarbene Species

Chemistry. 2021 Jun 10;27(33):8461-8467. doi: 10.1002/chem.202100195. Epub 2021 May 14.

Authors

Affiliations

¹ Department of Chemistry and Centre for Sustainable Chemistry, Ghent University, Krijgslaan 281-S3, 9000, Gent, Belgium.
² WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, Scotland.
³ EaStCHEM School of Chemistry, University of St Andrews, St Andrews, KY16 9ST, UK.
⁴ Departamento de Química Inorgánica, Universidad Autónoma de Madrid, 28049, Madrid, Spain.
⁵ Universita' di Salerno, Dipartimento di Chimica e Biologia, Via Papa Paolo Giovanni II, 84100, Fisiciano, SA, Italia.
⁶ Separation and Conversion Technology Unit, VITO (Flemish Institute for Technological Research), Boeretang 200, B-2400, Mol, Belgium.

PMID: 33822412
DOI: 10.1002/chem.202100195

Abstract

Readily prepared and bench-stable [Au(CF₃ )(NHC)] compounds were synthesized by using new methods, starting from [Au(OH)(NHC)], [Au(Cl)(NHC)] or [Au(L)(NHC)]HF₂ precursors (NHC=N-heterocyclic carbene). The mechanism of formation of these species was investigated. Consequently, a new and straightforward strategy for the mild and selective cleavage of a single carbon/fluorine bond from [Au(CF₃ )(NHC)] complexes was attempted and found to be reversible in the presence of an additional nucleophilic fluoride source. This straightforward technique has led to the unprecedented spectroscopic observation of a gold(I)-NHC difluorocarbene species.

Keywords: N-heterocyclic carbenes; difluorocarbenes; fluoride abstraction; gold(I); trifluoromethyl.

Grants and funding

BoF