Molybdenum Alkylidyne Silyloxy N‐Heterocyclic Carbene Complexes – Highly Active Alkyne Metathesis Catalysts that can be Handled in Air

• Published in: European journal of inorganic chemistry 2023-01, Vol.26 (3), p.n/a
• Main Authors: Musso, Janis V., Gramm, Vincent, Stein, Sarjano, Frey, Wolfgang, Buchmeiser, Michael R.
• Format: Article
• Language: English
• Subjects: Alkylidynes; Alkynes; Carbenes; Catalysts; Functional groups; Inorganic chemistry; Metathesis; Molybdenum; N-heterocyclic carbenes; NMR; Nuclear magnetic resonance; Silyloxy; Single crystals; Stability
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.202200649

A series of molybdenum alkylidyne silyloxy N‐heterocyclic carbene (NHC) complexes of the general formula [Mo(≡C(R))(OSiPh3)3(NHC)] (R=tBu, 4‐methoxyphenyl, 2,4,6‐trimethylphenyl; NHC = 1,3‐diisopropylimidazol‐2‐ylidene, 1,3‐dicyclohexylimidazol‐2‐ylidene, 1,3‐dicyclohexyl‐4,5‐dihydroimidazol‐2‐ylidene, 1,3‐dimethylimidazol‐2‐ylidene, 1,3‐dimethyl‐4,5‐dichloroimidazol‐2‐ylidene) was synthesized. Single crystal X‐ray analyses revealed that with increasing steric demand of the alkylidyne group, enhanced air‐stability of the complexes in the solid‐state is achieved with the most stable complex (R=2,4,6‐trimethylphenyl, NHC = 1,3‐diisopropylimidazol‐2‐ylidene) being stable in air for 24 h without showing signs of decomposition in 1H NMR. In contrast to previously reported air‐stable molybdenum‐based complexes, the novel catalysts proved to be highly active in alkyne metathesis, allowing for turnover numbers (TONs) of up to 6000 without further activation, and tolerant towards several functional groups such as tosyl, ether, ester, thioether and nitro moieties. Their air stability allows for facile handling of the catalysts in air and even after exposure to ambient atmosphere for one week, the most stable representative still displayed high productivity in alkyne metathesis. Molybdenum alkylidyne silyloxy NHC complexes are stable in air for up to 24 h, which allows for facile handling under ambient atmosphere. In addition, they possess remarkably high activity and functional group tolerance in alkyne metathesis. This renders them user‐friendly catalysts that can be employed as a tool in organic chemistry without the requirement of a glove box.