Cationic Tungsten Alkylidyne N‐Heterocyclic Carbene Complexes: Synthesis and Reactivity in Alkyne Metathesis

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 analogo...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2020-08, Vol.2020 (32), p.3070-3082
Main Authors: Hauser, Philipp M., Ende, Melita, Groos, Jonas, Frey, Wolfgang, Wang, Dongren, Buchmeiser, Michael R.
Format: Article
Language:English
Subjects:
Alkylidyne
Alkynes
Cations
Coordination compounds
Decomposition reactions
Inorganic chemistry
Metathesis
N‐Heterocyclic Carbenes
Tungsten
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Summary: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. The synthesis and reactivity of the first cationic tungsten alkylidyne NHC complexes as well as the synthesis of a cationic tungstacyclobutadiene is described.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.202000503