Cationic Tungsten Alkylidyne N‐Heterocyclic Carbene Complexes: Synthesis and Reactivity in Alkyne Metathesis
Year: 2020
Type: article
Abstract: The first cationic and neutral tungsten alkylidyne N‐heterocyclic carbene (NHC) complexes bearing one triflate ligand were synthesized and tested for their reactivity in alkyne metathesis. Both types of tungsten alkylidyne complexes display a higher productivity in alkyne metathesis than the analogous neutral tungsten alkylidyne NHC trisalkoxide complexes. Reaction of W(≡CC6H4OMe)(1,3‐bis(1‐hydroxy‐1,1‐trifluoromethylethyl)‐imidazol‐2‐ylidene)Cl (W18) with AgB(ArF)4 (ArF = 3,5‐bis(trifluoromethyl)phenyl) resulted in the unexpected formation of, to the best of our knowledge, the first cationic ditungstatetrahedrane W2(1,3‐bis(1‐hydroxy‐1,1‐trifluoromethyl‐ethyl)‐imidazol‐2‐ylidene)2(MeCN)(µ‐((Ar)CC(Ar)))+ (B(ArF)4)– (W19, Ar = C6H4OMe), which suggests bimolecular decomposition as a possible decomposition pathway of cationic tungsten alkylidyne NHC complexes. Reaction of the cationic tungsten alkylidyne NHC complex W(≡CC6H4OMe)(1,3‐diisopropylimidazol‐2‐ylidene)(OC(CF3)2Me)2(NCtBu)+ (B(ArF)4)– (W7) with 1‐phenyl‐1‐propyne allowed for the isolation of a cationic tungstacyclobutadiene W(C3(Ph)(Me)(C6H4OMe))(1,3‐diisopropylimidazol‐2‐ylidene)(OC(CF3)2Me)2(NCtBu)+ (B(ArF)4)– (W20). Its formation strongly supports a cationic active species in the alkyne metathesis with tungsten alkylidyne NHC complexes.
Institution: University of Stuttgart
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $3,500
Funder: Deutsche Forschungsgemeinschaft
OpenAlex ID: W3029645958