Synthesis and Reactivity of a Pentacoordinated Thiolate-Based Imido-Alkylidene W(VI) Complexes

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.

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

Hauser

Ende

Groos

et al. 2020

Eur J Inorg Chem

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N-Heterocyclic carbene-induced transmethylation in tungsten imido alkylidene bistriflates: unexpected formation of an N-heterocyclic olefin complex

2017

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The reaction of [W(N-2,6-PrCH)(CHCMePh)(OTf)(DME)] (DME = 1,2-dimethoxyethane, OTf = CFSO) with the N-heterocyclic carbene (NHC) 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene (IMesH) leads to DME activation followed by transmethylation and in due consequence to the formation of the N-heterocyclic olefin complex [W(N-2,6-PrCH)(CHCMePh)(OTf)(IMesHCH)] along with [W(N-2,6-PrCH)(CHCMePh)(OTf)(IMesH)(κ-O(CH)OMe)], [1,3-bis(2,4,6-trimethylphenyl)-2-methylimidazolidinium (OTf)] and [1,3-bis(2,4,6-trimethylphenyl)-2-H-imidazolidinium (OTf)]. A reaction pathway is proposed and confirmed by the use of C-labelled compounds; structures of the products were verified by NMR and/or single-crystal X-ray analysis.

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Editorial: Tribute to Yves Chauvin

Candel

2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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Synthesis and Reactivity of a Pentacoordinated Thiolate-Based Imido-Alkylidene W(VI) Complexes

Cited by 3 publications

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

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

N-Heterocyclic carbene-induced transmethylation in tungsten imido alkylidene bistriflates: unexpected formation of an N-heterocyclic olefin complex

Editorial: Tribute to Yves Chauvin

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