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New tungsten and molybdenum alkylidyne complexes bearing mono-, bi-, and tridentate N-heterocyclic carbenes (NHCs) have been synthesized. Formation of unprecedented structures in complexes bearing N-tert-butyl substituents on the imidazol(in)-2-ylidene was observed, leading to molybdenum complexes containing an abnormal carbene (Mo-4) and a bridging O,C,C-pincer ligand (Mo-10) and to a tungsten complex containing a cationic imidazolinium-tagged alkoxide forming an inner salt with an anionic tungsten center (W-5). Both the abnormal carbene binding in Mo-4 and the O,C,C-pincer-type structure of Mo-10 were confirmed by singlecrystal X-ray analysis, and the proposed structure of W-5 is supported by the single-crystal X-ray structure of a minor byproduct (W-8) formed during the synthesis of W-4, displaying the aforementioned inner-salt-like structure. The novel alkylidyne complexes were also investigated for their capability to form a previously postulated quasi-cationic species with a weakly coordinating anion (WCA) during the alkyne homometathesis of 1phenyl-1-propyne. Overall, incorporation of bidentate and strongly σ donating NHCs as well as introduction of better leaving groups did not lead to the expected increase in catalytic activity. Despite identical ligand spheres, changing from molybdenum to tungsten led to complete loss of activity in the bidentate systems.

The tetracoordinated cationic molybdenum alkylidyne N-heterocyclic carbene (NHC) complexes [Mo(CC 6 H 4 -p-OMe)(IMes)(OCMewere synthesized from the pentacoordinated progenitor Mo(CC 6 H 4 -p-OMe)(IMes)-(OCMe(CF 3 ) 2 ) 2 (OTf) (Mo4). Complexes Mo4−Mo6 were evaluated for their ability to catalyze the self-metathesis of several internal alkynes. The presence of a triflate group facilitates formation of a cationic species while preformation of the cationic molybdenum center in molybdenum alkylidyne NHC complexes indeed results in a strong increase in catalyst productivity and activity, also in the presence of functional groups, compared to previously reported neutral congeners. The most striking feature of this class of tetracoordinate cationic complexes is the excellent catalytic activity in the alkyne metathesis of non-protic substrates, thereby supporting our previously published proposal of a tetracoordinate cationic active species in alkyne metathesis formed from the neutral, pentacoordinate molybdenum alkylidyne NHC progenitors. Catalyst productivity, expressed as turnover number, reached 20 000 in the self-metathesis of 1-phenyl-1-propyne (S1) using Mo(CC 6 H 4 -p-OMe)(1,3-dimesitylimidazol-2ylidene)(OCMe(CF 3 ) 2 ) 2 [B(Ar F ) 4 ] (Mo6) and 5-(benzyloxy)-2-pentyne (S2) at catalyst loadings as low as 0.005 mol %.

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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