Abstract

A new type of molybdenum alkylidyne catalysts for alkyne metathesis is described, which is distinguished by an unconventional podand topology. These structurally well‐defined complexes are easy to make on scale and proved to be tolerant toward numerous functional groups; even certain protic substituents were found to be compatible. The new catalysts were characterized by X‐ray crystallography and by spectroscopic means, including 95Mo NMR.

Highlights

  • A new type of molybdenum alkylidyne catalysts for alkyne metathesis is described, which is distinguished by an unconventional podand topology

  • The discovery that triarylsilanolate ligands synergize exceedingly well with molybdenum alkylidynes marks a milestone in the development of alkyne metathesis.[1,2,3]

  • Substrates able to entail ligand exchange will eventually bring productive alkyne metathesis to a hold since catalyst 1 and congeners draw their excellent performance from a intact siloxide ligand sphere. It may not come as a surprise that the attempted metathesis reaction of a substrate as simple as 8 containing an unhindered primary alcohol basically met with failure (Scheme 1)

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Summary

Introduction

A new type of molybdenum alkylidyne catalysts for alkyne metathesis is described, which is distinguished by an unconventional podand topology.

Results
Conclusion

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