Detection of Ylide Formation between an Alkylidenecarbene and Acetonitrile by Femtosecond Transient Absorption Spectroscopy

Femtosecond laser flash photolysis of 3-(1a,9b-dihydro-1H-cyclopropa[l]phenanthren-1-ylidene)tetrahydrofuran produces singlet 3-oxacyclopentylidenecarbene which reacts with acetonitrile solvent to form an ylide. This is the first direct detection of ylide formation by an alkylidenecarbene. This new type of ylide was observed to have a broad absorption band in the visible region with lambda(max) similar to 450 nm and a lifetime of similar to 13.5 ps. As with other conventional carbenes (the divalent carbon atom is separately bound to two substituents), this ylide formation method could be also useful for detecting alkylidenecarbenes, especially those that do not absorb at wavelengths suitable for direct observation. Furthermore, the mechanisms by which 3-oxacyclopentylidenecarbene forms the ylide and the overall favorability of ylide formation, vis-a-vis ring expansion of the carbene to strained 3-oxacyclohexyne, were supported by results from density functional theory calculations.

Automated summary

Femtosecond laser flash photolysis of 3-(1a,9b-dihydro-1H-cyclopropa[l]phenanthren-1-ylidene)tetrahydrofuran produces a singlet 3-oxacyclopentylidenecarbene which reacts with acetonitrile solvent to form an ylide. This new type of ylide has a broad absorption band in the visible region with lambda(max) around 450 nm and a lifetime of approximately 13.5 ps.